Electrolytic tank diagnosis method and related device
By superimposing AC excitation signals onto the electrolyzer to obtain voltage and current sequences, and calculating impedance data and electrochemical parameters, the lag problem in the diagnosis of electrolyzer operating status is solved, and online real-time diagnosis of the electrolyzer is realized.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-02-10
- Publication Date
- 2026-04-10
AI Technical Summary
In the existing technology, the method for diagnosing the operating status of electrolytic cells is offline detection, which results in a delayed response and makes it impossible to determine the operating status of the electrolytic cells in a timely manner.
By superimposing an AC excitation signal onto the electrolyzer, obtaining voltage and current sequences based on the sampling time sequence, calculating impedance data, and determining the set of electrochemical parameters, online continuous monitoring of the electrochemical process in the electrolyzer can be achieved.
It improves the real-time diagnostic capability of electrolytic cell operation status, accurately reflects changes in electrochemical parameters, and enables online real-time diagnosis of electrolytic cells.
Smart Images
Figure CN121826802A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of electrochemistry, and in particular to an electrolytic cell diagnosis method and related device. BACKGROUND
[0002] As a core component of water electrolysis hydrogen production, fuel cell and other energy conversion equipment, the running state of the electrolytic cell directly affects the efficiency and stability of the system.
[0003] In related technologies, the running state of the electrolytic cell is usually diagnosed by offline detection methods such as disassembly analysis and sampling detection. However, the offline detection method has a relatively lagging response, which makes it impossible to determine the running state of the electrolytic cell in a timely manner. SUMMARY
[0004] To solve the above problems, the present application provides an electrolytic cell diagnosis method and related device for improving the online continuous detection of the electrochemical process changes of the electrolytic cell.
[0005] Based on this, the present application discloses the following technical solutions: In a first aspect, the present application provides an electrolytic cell diagnosis method, which comprises: The driving unit is configured to superimpose an alternating excitation signal on the electrolytic cell, and based on a sampling time sequence corresponding to the alternating excitation signal, obtain a voltage sequence at the i+1 moment and a current sequence at the i+1 moment of the electrolytic cell, i being a positive integer; The determination unit is configured to determine impedance data of the electrolytic cell at the i+1 moment according to the voltage sequence at the i+1 moment and the current sequence at the i+1 moment; The determination unit is configured to determine an electrochemical parameter set at the i+1 moment according to the impedance data at the i+1 moment, the electrochemical parameters included in the electrochemical parameter set being used to represent the electrochemical process of the electrolytic cell; The determination unit is configured to determine a diagnosis result of the electrolytic cell according to the difference between the electrochemical parameter set at the i+1 moment and the electrochemical parameter set at the i moment.
[0006] In a second aspect, the present application provides an electrolytic cell diagnosis device, which comprises: The excitation unit is configured to superimpose an alternating excitation signal on the electrolytic cell, and based on a sampling time sequence corresponding to the alternating excitation signal, obtain a voltage sequence at the i+1 moment and a current sequence at the i+1 moment of the electrolytic cell, i being a positive integer; The determination unit is configured to determine impedance data of the electrolytic cell at the i+1 moment according to the voltage sequence at the i+1 moment and the current sequence at the i+1 moment; The determination unit is configured to determine an electrochemical parameter set at the i+1 moment according to the impedance data at the i+1 moment, the electrochemical parameters included in the electrochemical parameter set being used to represent the electrochemical process of the electrolytic cell; a diagnosis unit configured to determine a diagnosis result of the electrolytic cell according to a difference between the set of electrochemical parameters at the i+1th moment and the set of electrochemical parameters at the ith moment.
[0007] In a third aspect, an embodiment of the present application provides a controller, the controller comprising a processor and a memory: The memory is configured to store a computer program and transmit the computer program to the processor. The processor is configured to execute the method of the first aspect.
[0008] In a fourth aspect, an embodiment of the present application provides a computer readable storage medium configured to store a computer program, the computer program being configured to execute the method of the first aspect.
[0009] In a fifth aspect, an embodiment of the present application provides a computer program product comprising a computer program, which, when executed on a computer device, causes the computer device to execute the method of the first aspect.
[0010] To sum up, the electrolytic cell diagnosis method provided by the embodiments of the present application, after driving the superposition of the alternating excitation signal for the electrolytic cell, based on the sampling time sequence corresponding to the alternating excitation signal, the voltage sequence at the i+1th moment and the current sequence at the i+1th moment of the electrolytic cell are obtained, i is a positive integer, so that the voltage sequence and the current sequence responding to the alternating excitation signal are kept synchronous in the time dimension, which is conducive to accurately reflecting the real response characteristics of the electrolytic cell under the corresponding frequency of the alternating excitation signal, thereby improving the accuracy and real-time performance of the impedance data calculation. According to the voltage sequence at the i+1th moment and the current sequence at the i+1th moment, the impedance data of the electrolytic cell at the i+1th moment is determined. According to the impedance data at the i+1th moment, the set of electrochemical parameters at the i+1th moment is determined, and the electrochemical parameters included in the set of electrochemical parameters are used to characterize the electrochemical process of the electrolytic cell. By determining the impedance data and extracting the set of electrochemical parameters moment by moment, the online continuous detection of the change of the electrochemical process of the electrolytic cell is realized. According to the difference between the set of electrochemical parameters at the i+1th moment and the set of electrochemical parameters at the ith moment, the diagnosis result of the electrolytic cell is determined, so that the change trend of the running state of the electrolytic cell in the time dimension can be identified, the diagnosis result pays more attention to the change of the running state of the electrolytic cell reflected by the change of the electrochemical parameters, and thus the online real-time diagnosis of the electrolytic cell is realized. BRIEF DESCRIPTION OF DRAWINGS
[0011] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required by the embodiments or prior art description. Obviously, the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can also be obtained without creative labor on the basis of these drawings.
[0012] Figure 1 A flowchart of a diagnosis method of an electrolytic cell provided by an embodiment of the present application; Figure 2 A structural diagram of a diagnosis device of an electrolytic cell provided by an embodiment of the present application; Figure 3 A structural diagram of a controller provided by an embodiment of the present application. DETAILED DESCRIPTION
[0013] The embodiments of the present application will be described in more detail with reference to the drawings. Although some embodiments of the present application are shown in the drawings, it should be understood that the present application can be implemented in various forms, and should not be interpreted as being limited to the embodiments set forth herein, but rather, these embodiments are provided to make the present application more thorough and complete. It should be understood that the drawings and embodiments of the present application are only for exemplary purposes, and are not intended to limit the scope of protection of the present application.
[0014] Electrochemical impedance spectroscopy (EIS) technology, as a non-destructive testing method, is widely used in performance analysis and state evaluation of electrochemical devices. In the related art, an alternating excitation signal is applied point by point in a predetermined frequency range, and the corresponding voltage response and current response are collected, so as to obtain a set of impedance data covering all frequencies, and the running state of the electrolytic cell is diagnosed based on the impedance data. This diagnosis method has a basic assumption: the running state of the measured object (i.e. the electrolytic cell) remains basically unchanged during the completion of a complete frequency sweep measurement, so the impedance data obtained by a complete frequency sweep can be regarded as a whole description of the running state of the electrolytic cell.
[0015] However, the working current, temperature, reaction interface state and mass transfer condition of the electrolytic cell will change continuously over time. For example, during the complete frequency sweep including the low frequency measurement point, the measurement period usually lasts for several minutes, and during this period, the running state of the electrolytic cell has changed, so that the system states corresponding to the start stage and the end stage of the frequency sweep are inconsistent. The impedance data obtained thereby essentially reflects the superposition of the running states at different times, rather than the true state at a certain time, thereby weakening the instantaneous characterization ability of the impedance data for the running state of the electrolytic cell.
[0016] Based on this, the embodiment of the present application provides an electrolytic cell diagnosis method and related device, superimposes an alternating excitation signal on the electrolytic cell, obtains the voltage sequence of the i+1 moment of the electrolytic cell and the current sequence of the i+1 moment of the electrolytic cell based on the sampling time sequence corresponding to the alternating excitation signal, i is a positive integer, so that the voltage sequence and the current sequence responding to the alternating excitation signal remain synchronous in the time dimension, which is conducive to accurately reflecting the real response characteristics of the electrolytic cell under the corresponding frequency of the alternating excitation signal, thereby improving the accuracy and real-time performance of the impedance data calculation. According to the voltage sequence of the i+1 moment and the current sequence of the i+1 moment, the impedance data of the electrolytic cell at the i+1 moment is determined. According to the impedance data of the i+1 moment, the set of electrochemical parameters of the i+1 moment is determined, and the electrochemical parameters included in the set of electrochemical parameters are used to characterize the electrochemical process of the electrolytic cell. By determining the impedance data and extracting the set of electrochemical parameters moment by moment, the online continuous detection of the change of the electrochemical process of the electrolytic cell is realized. According to the difference between the set of electrochemical parameters of the i+1 moment and the set of electrochemical parameters of the i moment, the diagnosis result of the electrolytic cell is determined, so that the change trend of the running state of the electrolytic cell in the time dimension can be identified, the diagnosis result pays more attention to the change of the running state of the electrolytic cell reflected by the electrochemical parameters, and thus the online real-time diagnosis of the electrolytic cell is realized.
[0017] The electrolytic cell diagnosis method provided by the present application can be applied to a computer device with electrolytic cell diagnosis capability, such as a terminal device, a server. The terminal device can be a desktop computer, a notebook computer, a mobile phone and a tablet computer, etc.; the server can be a stand-alone physical server, or a server cluster or distributed system composed of multiple physical servers, etc. The terminal device and the server can be directly or indirectly connected through wired or wireless communication, which is not limited in the present application.
[0018] Referring to Figure 1 , the figure is a flowchart of the electrolytic cell diagnosis method provided by the embodiment of the present application. In order to facilitate description, the following embodiments take the server as an example to introduce the execution subject of the electrolytic cell diagnosis method. As Figure 1 shown, the electrolytic cell diagnosis method comprises S101-S104.
[0019] S101: driving to superimpose an alternating excitation signal on the electrolytic cell, obtaining the voltage sequence of the i+1 moment of the electrolytic cell and the current sequence of the i+1 moment of the electrolytic cell based on the sampling time sequence corresponding to the alternating excitation signal.
[0020] The alternating excitation signal is a kind of excitation signal superimposed on the working current of the electrolytic cell during normal operation of the electrolytic cell to excite the current response and voltage response of the electrolytic cell to the alternating excitation signal. The alternating excitation signal can be multi-frequency. The amplitude of the alternating excitation signal is small relative to the direct current working voltage or working current of the electrolytic cell to avoid having a substantial impact on the electrolysis reaction process.
[0021] The sampling timing is a time reference for indicating the correspondence between the application time of the alternating excitation signal and the sampling time of the voltage signal and the current signal. Based on the sampling timing, the voltage sequence and the current sequence can be determined to correspond to the same time, improving the time consistency of subsequent impedance data calculation. i is a positive integer. It should be noted that each time mentioned in the present application is the corresponding time of the sampling period, and the time can be a time point, or the time can be used to represent a sampling period, which will not be described in detail hereinafter.
[0022] The voltage sequence is an ordered data set formed by a plurality of voltage sampling values obtained by continuous sampling, and the current sequence is an ordered data set formed by a plurality of current sampling values obtained by continuous sampling. The voltage sequence and the current sequence correspond to each other in the time dimension, and are used to represent the dynamic response of the electrolytic cell under the action of the alternating excitation.
[0023] Exemplarily, the excitation signal generation module can generate an alternating excitation signal with controllable amplitude and adjustable frequency. Specifically, the excitation signal generation module can generate a sinusoidal alternating excitation signal based on a direct digital frequency synthesis technology or a programmable waveform generator, and the frequency of the alternating excitation signal is within a preset frequency range, which can be configured according to the diagnosis requirements. To avoid the influence of the alternating excitation signal on the direct current working state of the electrolytic cell, the alternating excitation signal can be superimposed into the main power loop of the electrolytic cell through a coupling circuit, which can be a direct current isolation capacitor or a transformer, to realize the decoupling of the alternating excitation signal and the direct current signal.
[0024] At the same time of superimposing the alternating excitation signal, the voltage response and the current response of the electrolytic cell are synchronously collected based on the sampling timing corresponding to the alternating excitation signal. The collection of the voltage response can be realized through a voltage sensing and conditioning circuit, which for example includes a high-precision differential amplifier for collecting and filtering and amplifying the alternating voltage signal between the two ends of the electrolytic cell. The collection of the current response can be realized through a current sensing and conditioning circuit, which for example includes a sampling resistor or a current sensor for collecting and filtering and amplifying the alternating current signal between the two ends of the electrolytic cell. The conditioned voltage signal and the current signal can be synchronously collected by an analog-to-digital converter to obtain the voltage sequence at the i+1 time and the current sequence at the i+1 time.
[0025] S102: Determine impedance data of the electrolytic cell at the i+1th moment according to the voltage sequence at the i+1th moment and the current sequence at the i+1th moment.
[0026] The impedance data is used to characterize the relationship between the voltage sequence and the current sequence of the electrolytic cell under the action of the alternating excitation signal. The impedance data can at least include corresponding impedance amplitude information and / or phase information at each frequency. The impedance data can be represented in the form of complex numbers, amplitude and phase, or equivalent data, to reflect the electrochemical characteristics of the electrolytic cell at the corresponding frequency.
[0027] By processing the voltage sequence at the i+1th moment and the current sequence at the i+1th moment, the voltage response component and the current response component of the electrolytic cell under the action of the alternating excitation signal can be extracted, and the impedance data can be determined based on the relationship between the two. Since the voltage sequence and the current sequence are both synchronously collected at the same sampling time sequence, the impedance data calculated therefrom can accurately reflect the actual response characteristics of the electrolytic cell at the i+1th moment.
[0028] In one possible implementation, the voltage sequence includes a plurality of frequency sub-voltage sequences, and the current sequence includes a plurality of frequency sub-current sequences, i.e., sub-voltage sequences and sub-current sequences corresponding to the plurality of frequency alternating excitation signals. The target frequency is one of the plurality of frequencies. The determination process of the impedance data is exemplarily described taking the target frequency in the i+1th moment as an example: The sub-voltage sequence of the target frequency and the sub-current sequence of the target frequency are obtained. A reference signal corresponding to the alternating excitation signal is generated based on the target frequency. The reference signal is a signal generated according to the target frequency, corresponding to the alternating excitation signal in frequency, and used as a reference for correlation operation. The reference signal can be a sine signal, a cosine signal, or an equivalent signal related to the alternating excitation signal in frequency and phase relationship.
[0029] The sub-voltage sequence of the target frequency is correlated with the reference signal to obtain the voltage correlation result of the target frequency, and the sub-current sequence of the target frequency is correlated with the reference signal to obtain the current correlation result of the target frequency. The impedance data of the target frequency is determined according to the voltage correlation result of the target frequency and the current correlation result of the target frequency.
[0030] The correlation operation is an operation process of performing operation processing on the collected sub-voltage sequence or sub-current sequence and the reference signal to extract the frequency component corresponding to the reference signal in the collected signal. Through the correlation operation, noise components and other frequency components irrelevant to the target frequency can be suppressed, so as to obtain a correlation result reflecting the target frequency response characteristic. The voltage correlation result is a result obtained by performing correlation operation on the sub-voltage sequence and the reference signal, and is used to represent the voltage response characteristic of the electrolytic cell at the target frequency. The current correlation result is a result obtained by performing correlation operation on the sub-current sequence and the reference signal, and is used to represent the current response characteristic of the electrolytic cell at the target frequency.
[0031] By decomposing the voltage sequence and the current sequence according to the frequency, and extracting the voltage response result and the current response result for a specific frequency respectively, the impedance data at the frequency can be accurately determined.
[0032] Each frequency can be taken as a target frequency, and the above process can be performed to obtain the impedance data of each frequency, so as to obtain the impedance data of the electrolytic cell at the i+1 moment.
[0033] As a possible implementation manner, the Nyquist diagram or the Bode diagram at the i+1 moment can be obtained according to the impedance data at each frequency at the i+1 moment.
[0034] In the online real-time diagnosis scene of the electrolytic cell, it is necessary to obtain the impedance data reflecting the current state of the electrolytic cell as soon as possible during the continuous operation of the electrolytic cell. The frequency spectrum analysis method based on fast Fourier transform usually needs to complete a fixed length of data collection before the signal in the time period can be transformed in the whole frequency domain, and the frequency resolution is strongly related to the sampling time window. In the low frequency measurement, a long data waiting time is inevitably introduced, which leads to a significant time lag of the diagnosis result. In contrast, the reference signal is generated based on the target frequency in the embodiment of the application, and the correlation operation is performed on the collected sub-voltage sequence and sub-current sequence. Only the response component of the target frequency required for diagnosis needs to be extracted, and the calculation result can be accumulated gradually in the sampling process without waiting for the complete time window, so that the impedance data used for diagnosis can be obtained faster, and the state diagnosis demand under the online and real-time operation condition of the electrolytic cell is more suitable.
[0035] S103: Determine the set of electrochemical parameters at the i+1 moment according to the impedance data at the i+1 moment.
[0036] The set of electrochemical parameters includes at least one electrochemical parameter, and the electrochemical parameter is used to characterize the electrochemical process of the electrolytic cell. The electrochemical process of the electrolytic cell is a process related to the conversion of electrical energy and chemical energy occurring during the operation of the electrolytic cell, including but not limited to electrolyte conduction process, electrode interface reaction process, and process related to mass transfer. The set of electrochemical parameters is used to quantitatively describe the above processes. For example, the electrochemical parameter can be a parameter related to electrolyte conduction, interface reaction, charge transfer or mass transfer process. Different electrochemical parameters correspond to different physical or chemical meanings, thereby being used to describe the operating state of the electrolytic cell from different angles.
[0037] The set of electrochemical parameters at the i+1 moment is a set of electrochemical parameters determined based on the impedance data corresponding to the i+1 moment, and is used to characterize the operating state of the electrolytic cell at the i+1 moment. The set of electrochemical parameters at the i+1 moment and the set of electrochemical parameters at the i moment are distinguished from each other in the time dimension, and can be used for subsequent analysis of the change of the operating state of the electrolytic cell.
[0038] The impedance data can reflect the response relationship between the voltage sequence and the current sequence of the electrolytic cell under different frequency conditions, thereby indirectly characterizing the electrochemical characteristics of the electrolytic cell. By determining the set of electrochemical parameters based on the impedance data, the frequency-dependent impedance data can be converted into electrochemical parameters corresponding to the internal electrochemical process of the electrolytic cell.
[0039] The embodiments of the present application do not specifically limit the determination of the set of electrochemical parameters at the i+1 moment based on the impedance data at the i+1 moment, which is described below in three ways.
[0040] The first way is parameter fitting.
[0041] A plurality of initial electrochemical parameters are obtained. The plurality of initial electrochemical parameters are fitted according to the impedance data at the i+1 moment, to obtain the set of electrochemical parameters at the i+1 moment.
[0042] The initial electrochemical parameter is a parameter used to characterize the electrochemical process of the electrolytic cell and has not been fitted numerically.
[0043] Exemplarily, an equivalent circuit model capable of characterizing the electrochemical process of the electrolytic cell can be established for the electrolytic cell, and the equivalent circuit model includes a plurality of initial electrochemical parameters. The measured impedance data at the i+1 moment is fitted to the equivalent circuit model, thereby determining the actual value of each initial electrochemical parameter in the equivalent circuit model, and thereby obtaining the set of electrochemical parameters including a plurality of electrochemical parameters.
[0044] Thus, the initial electrochemical parameters can pre-describe each electrochemical process in the electrolytic cell in a parameter form before fitting, so that the processing of the impedance data is no longer a post-analysis of the measurement results, but a fitting of the parameter values within the pre-set electrochemical process framework, thereby improving the efficiency and accuracy of determining the electrochemical parameters.
[0045] Option two, feature extraction is performed on the impedance data.
[0046] A feature vector related to a specific frequency interval or a specific impedance feature can be extracted from the impedance data, and the feature vector can be used as an electrochemical parameter. For example, the impedance data can be input into a pre-trained feature extraction model to obtain the corresponding electrochemical parameter. The feature extraction model can be trained by impedance data samples and electrochemical parameter samples.
[0047] Option three, determination based on a mapping relationship between the impedance data and the electrochemical parameters.
[0048] A mapping relationship between the impedance data and the electrochemical parameters can be pre-established, and the impedance data can be converted into a corresponding set of electrochemical parameters based on the mapping relationship. The mapping relationship can be constructed based on historical data, simulation data or experimental data, and used to quickly determine the electrochemical parameters during online diagnosis.
[0049] S104: Determine the diagnosis result of the electrolytic cell according to the difference between the set of electrochemical parameters at the i+1 moment and the set of electrochemical parameters at the i moment.
[0050] The present embodiment takes the i+1 moment as the current moment for diagnosis, and takes the i moment as the last moment when the set of electrochemical parameters is determined, so that the changes in the electrochemical process of the electrolytic cell between the i moment and the i+1 moment can be reflected according to the difference between the sets of electrochemical parameters, thereby enabling online real-time diagnosis of the electrolytic cell.
[0051] If there is no difference between the set of electrochemical parameters at the i+1 moment and the set of electrochemical parameters at the i moment, the diagnosis result of the electrolytic cell can be maintained as the diagnosis result at the i moment. If there is a difference between the set of electrochemical parameters at the i+1 moment and the set of electrochemical parameters at the i moment, the change process of the corresponding electrochemical process can be determined based on the electrochemical parameters that have the difference, and the diagnosis result of the electrolytic cell at the i+1 moment can be determined.
[0052] The present embodiment does not specifically limit how to determine the diagnosis result of the electrolytic cell, which will be described in detail in other embodiments.
[0053] It can be seen from the above technical solution that after the alternating excitation signal is superimposed on the electrolytic cell, based on the sampling timing corresponding to the alternating excitation signal, the voltage sequence at the i+1 time and the current sequence at the i+1 time of the electrolytic cell are obtained, i is a positive integer, so that the voltage sequence and the current sequence responding to the alternating excitation signal are kept synchronous in the time dimension, which is beneficial to accurately reflecting the real response characteristics of the electrolytic cell under the corresponding frequency of the alternating excitation signal, thereby improving the accuracy and real-time performance of the impedance data calculation. According to the voltage sequence at the i+1 time and the current sequence at the i+1 time, the impedance data of the electrolytic cell at the i+1 time is determined. According to the impedance data at the i+1 time, the electrochemical parameter set at the i+1 time is determined, and the electrochemical parameters included in the electrochemical parameter set are used to characterize the electrochemical process of the electrolytic cell. By determining the impedance data and extracting the electrochemical parameter set at each time, the online continuous detection of the change of the electrochemical process of the electrolytic cell is realized. According to the difference between the electrochemical parameter set at the i+1 time and the electrochemical parameter set at the i time, the diagnosis result of the electrolytic cell is determined, so that the change trend of the running state of the electrolytic cell in the time dimension can be identified, the diagnosis result pays more attention to the change of the running state of the electrolytic cell reflected by the electrochemical parameters, and thus the online real-time diagnosis of the electrolytic cell is realized.
[0054] In a possible implementation, the diagnosis target can be obtained. The target electrochemical parameter corresponding to the diagnosis target in the electrochemical parameter set is determined. According to the difference between the target electrochemical parameter at the i+1 time and the target electrochemical parameter at the i time, the diagnosis result of the electrolytic cell is determined.
[0055] The diagnosis target is a specific object concerned about the running state of the electrolytic cell, which can include a component of the electrolytic cell and also can include its state. For example, the diagnosis target can be a diaphragm, and for another example, the diagnosis target can be the attenuation of a catalyst. The target electrochemical parameter is at least one electrochemical parameter in the electrochemical parameter set corresponding to the diagnosis target and having a characterization significance for the diagnosis target. That is, not all electrochemical parameters in the electrochemical parameter set are used to determine the diagnosis result of the electrolytic cell, but the target electrochemical parameter is determined based on the diagnosis target. According to the difference between the target electrochemical parameter at the i+1 time and the target electrochemical parameter at the i time, the diagnosis result of the electrolytic cell is determined.
[0056] Exemplarily, the diagnosis target and the electrochemical parameter can be pre-set with a parameter correspondence relationship, and based on the parameter correspondence relationship, the target electrochemical parameter corresponding to the diagnosis target can be quickly determined.
[0057] Therefore, in the diagnosis process, it is not necessary to compare all the electrochemical parameters, but only the target electrochemical parameter corresponding to the diagnosis target needs to be compared, which not only reduces the calculation amount and improves the diagnosis efficiency, but also excludes the electrochemical parameters irrelevant to the diagnosis target in the diagnosis process, thereby improving the accuracy of the diagnosis basis.
[0058] In a possible implementation, the electrochemical parameters included in the set of electrochemical parameters include at least one of a solution resistance, a charge transfer resistance, an amplitude parameter of a constant phase element, an index parameter of the constant phase element, and a diffusion impedance coefficient.
[0059] The solution resistance is an ohmic resistance of an electrolyte solution and a conductive path thereof in the electrolytic tank when current passes through, and the solution resistance can be determined by factors such as the conductivity of the electrolyte, the flow channel structure, and the distance between the electrodes. The charge transfer resistance is an impedance component corresponding to the charge transfer process of electrons and ions when an electrochemical reaction occurs at the interface between the electrode and the electrolyte, and is used to describe the resistance characteristics in the interface reaction process. The amplitude parameter of the constant phase element is a parameter in a constant phase element model, which is used to describe the scale factor of the impedance amplitude of the element varying with frequency, and the amplitude parameter of the constant phase element is related to the strength of the capacitive response of the interface. The index parameter of the constant phase element is a parameter in a constant phase element model, which is used to describe the index factor of the impedance of the constant phase element varying with frequency, and is used to reflect the degree of deviation of the element from the ideal capacitive behavior. The diffusion impedance coefficient is a parameter used to describe the impedance characteristics introduced by the diffusion process in the electrochemical system, and generally corresponds to the impedance component related to the diffusion process in the low-frequency region of the impedance spectrum.
[0060] The following takes five diagnosis modes as examples to exemplarily illustrate the diagnosis process.
[0061] The diagnosis mode one is that if the diagnosis target is used to diagnose the attenuation of the catalyst, the target electrochemical parameter corresponding to the diagnosis target in the set of electrochemical parameters is determined to be the charge transfer resistance.
[0062] The diagnosis result of the electrolytic tank is determined according to the difference between the charge transfer resistance at the i+1 time and the charge transfer resistance at the i time. Wherein, the increase of the charge transfer resistance is used to indicate the decrease of the activity of the catalyst.
[0063] When the catalyst attenuates, the effective reaction sites on the electrode surface decrease, the interface reaction rate decreases, and thus the charge transfer resistance changes. By comparing the change of the charge transfer resistance at adjacent times, the change trend of the catalytic performance of the electrode can be reflected.
[0064] By diagnosing based on the change of charge transfer resistance, the catalyst performance change can be continuously monitored during the operation of the electrolytic cell, and the decay trend can be judged without relying on the absolute parameter threshold, which is conducive to realizing the real-time perception of the early performance decline of the catalyst and improving the sensitivity and timeliness of online diagnosis.
[0065] As a possible implementation, the decay of the catalyst can also be comprehensively judged in combination with the parameter related to the roughness or unevenness of the catalyst surface in the constant phase element. Specifically, the changes of the charge transfer resistance and the exponential parameter of the constant phase element at adjacent moments can be compared at the same time. When the charge transfer resistance increases and the exponential parameter of the constant phase element decreases, it is determined that the possibility of catalyst decay is high. When only the charge transfer resistance changes and the exponential parameter of the constant phase element remains basically unchanged, it is determined that the parameter change is caused by short-term working condition fluctuations.
[0066] The second diagnosis method, if the diagnosis target is used to diagnose the diaphragm, the target electrochemical parameter corresponding to the diagnosis target in the set of electrochemical parameters is determined to be the solution resistance.
[0067] According to the difference between the solution resistance at the i+1 moment and the solution resistance at the i moment, the diagnosis result of the electrolytic cell is determined. Wherein, the abnormal increase of the solution resistance is used to indicate the diaphragm gap blockage, the adsorption of pollution ions or the change of electrolyte concentration.
[0068] When the diaphragm gap is blocked, the pollution ions are adsorbed or the electrolyte concentration is changed, the current conduction path is limited, thereby causing the change of the solution resistance. By comparing the solution resistances at different moments, the change of the diaphragm related conduction condition can be reflected.
[0069] Based on the change of the solution resistance, the running state of the diaphragm can be judged online without disassembling the equipment, which is suitable for quickly obtaining diagnosis information under the condition of running condition fluctuation, thereby improving the real-time and convenience of the online diagnosis of the diaphragm state.
[0070] The third diagnosis method, if the diagnosis target is used to diagnose the diaphragm, the target electrochemical parameter corresponding to the diagnosis target in the set of electrochemical parameters is determined to be the diffusion impedance coefficient.
[0071] According to the difference between the diffusion impedance coefficient at the i+1 moment and the diffusion impedance coefficient at the i moment, the diagnosis result of the electrolytic cell is determined. Wherein, the increase of the diffusion impedance coefficient is used to indicate the increase of the diffusion resistance of ions in the diaphragm channel.
[0072] When the diffusion of ions in the diaphragm channel is hindered, the influence of the diffusion process on the impedance is enhanced, thereby causing the change of the diffusion impedance coefficient. By analyzing the change of the diffusion impedance coefficient at adjacent moments, the change of the mass transfer state inside the diaphragm can be reflected.
[0073] By supplementally diagnosing the diaphragm state from the dimension of the mass transfer process, it is beneficial to improve the recognition accuracy and stability of the abnormal state of the diaphragm in the online diagnosis process by avoiding relying on a single conductive parameter for judgment.
[0074] The fourth diagnosis manner is to obtain a diagnosis model. The electrochemical parameter set at the i+1 moment and the electrochemical parameter set at the i moment are input into the diagnosis model to obtain a diagnosis result of the electrolytic cell.
[0075] The diagnosis model is obtained based on different types of electrochemical parameter samples at different moments and diagnosis result labels.
[0076] The diagnosis result label is a true diagnosis result labeled for the electrochemical parameter sample. In the training process of the diagnosis model, different types of electrochemical parameter samples at different moments can be input into an initial diagnosis model (a diagnosis model that has not been trained) to obtain different types of predicted diagnosis results at different moments. The difference between the predicted diagnosis result and the diagnosis result label is used to adjust the difference of the initial diagnosis model to obtain the diagnosis model.
[0077] The embodiments of the present application do not specifically limit the form of the diagnosis model, which can be a support vector machine, a neural network, etc.
[0078] Therefore, the diagnosis model trained based on different types of electrochemical parameter samples at different moments is introduced, and the electrochemical parameter sets at the i+1 moment and the i moment are jointly used as the input of the diagnosis model for diagnosis, which can make the diagnosis process no longer rely on a single parameter or a preset threshold for judgment, but consider the change relationship of multiple electrochemical parameters in the time dimension, thereby improving the recognition ability of complex state changes.
[0079] The fifth diagnosis manner is to obtain a standard electrochemical parameter set.
[0080] The health state information of the target component set in the electrolytic cell is determined according to the difference between the electrochemical parameter set at the i+1 moment and the standard electrochemical parameter. The service life diagnosis result of the electrolytic cell is determined according to the health state information of the target component set.
[0081] The standard electrochemical parameter set includes multiple standard electrochemical parameters for representing the normal operation condition of the electrolytic cell. The target component set includes at least one component, and the difference between the electrochemical parameter of the at least one component and the corresponding standard electrochemical parameter is greater than a difference threshold. The health state information is a state description information for representing the current operation state of the component, which is used to reflect the performance retention degree or the attenuation degree of the component. The service life diagnosis result is used to represent the remaining available time length of the electrolytic cell.
[0082] Exemplarily, components with a difference greater than a difference threshold from corresponding standard electrochemical parameters are determined as a target component set. Different electrochemical parameters can correspond to different difference thresholds. For components included in the target component set, it is determined according to the size of the difference that the component is in a mild attenuation state or an obvious attenuation state, so as to obtain health state information corresponding to the target component.
[0083] Health state information corresponding to each component of the target component set can be obtained, and the life state of the electrolytic cell as a whole is determined based on the health state information of each component. For example, when at least one target component in the target component set is in an obvious attenuation state, a life diagnosis result that the electrolytic cell is in a late life stage is determined. When each component in the target component set is in a normal state or a mild attenuation state, a life diagnosis result that the electrolytic cell is in a normal life stage is determined.
[0084] In this way, based on the set of standard electrochemical parameters, it can be determined whether each component is in a healthy state at each moment, and the life diagnosis result of the electrolytic cell is comprehensively determined, without the need to obtain historical data, so that real-time diagnosis can be performed.
[0085] Referring to Figure 2 , Figure 2 A kind of electrolytic cell diagnostic device provided in the embodiment of the application, device 200 includes: Excitation unit 201, for driving is superimposed on electrolytic cell AC excitation signal, based on the sampling time sequence corresponding to the AC excitation signal, the voltage sequence of the i+1 moment of the electrolytic cell and the current sequence of the i+1 moment are acquired, i is positive integer; Determination unit 202, for determining the impedance data of the electrolytic cell at the i+1 moment according to the voltage sequence of the i+1 moment and the current sequence of the i+1 moment; The determination unit 202, for determining the electrochemical parameter set of the i+1 moment according to the impedance data of the i+1 moment, the electrochemical parameter included in the electrochemical parameter set is used to characterize the electrochemical process of the electrolytic cell; Diagnosis unit 203, for determining the diagnosis result of the electrolytic cell according to the difference between the electrochemical parameter set of the i+1 moment and the electrochemical parameter set of the i moment.
[0086] Optionally, the voltage sequence includes a plurality of frequency sub-voltage sequences, and the current sequence includes a plurality of frequency sub-current sequences, and the determination unit 202 is specifically configured to: For the i+1 moment, the sub-voltage sequence of the target frequency and the sub-current sequence of the target frequency are acquired, and the target frequency is one of the plurality of frequencies; A reference signal corresponding to the AC excitation signal is generated based on the target frequency. correlate the sub-voltage sequence of the target frequency with the reference signal to obtain a voltage correlation result of the target frequency, and correlate the sub-current sequence of the target frequency with the reference signal to obtain a current correlation result of the target frequency; determine impedance data of the target frequency according to the voltage correlation result of the target frequency and the current correlation result of the target frequency; respectively take each frequency as the target frequency to obtain impedance data of the electrolytic cell at the i+1 moment.
[0087] Optionally, the determination unit 202 is specifically configured to: obtain a plurality of initial electrochemical parameters, the initial electrochemical parameters being electrochemical parameters that have not been fitted; fit the plurality of initial electrochemical parameters according to the impedance data of the i+1 moment to obtain a set of electrochemical parameters of the i+1 moment.
[0088] Optionally, the diagnosis unit 203 is specifically configured to: obtain a diagnosis target; determine a target electrochemical parameter corresponding to the diagnosis target in the set of electrochemical parameters; determine a diagnosis result of the electrolytic cell according to a difference between the target electrochemical parameter of the i+1 moment and the target electrochemical parameter of the i moment.
[0089] Optionally, the electrochemical parameters included in the set of electrochemical parameters include at least one of a solution resistance, a charge transfer resistance, an amplitude parameter of a constant phase element, an index parameter of a constant phase element, and a diffusion impedance coefficient.
[0090] Optionally, if the diagnosis target is used to diagnose the attenuation of a catalyst, the determination unit 202 is specifically configured to: determine that the target electrochemical parameter corresponding to the diagnosis target in the set of electrochemical parameters is the charge transfer resistance; the diagnosis unit 203 is specifically configured to: determine a diagnosis result of the electrolytic cell according to a difference between the charge transfer resistance of the i+1 moment and the charge transfer resistance of the i moment; wherein an increase in the charge transfer resistance indicates a decrease in the activity of the catalyst; if the diagnosis target is used to diagnose a diaphragm, the determination unit 202 is specifically configured to: determine that the target electrochemical parameter corresponding to the diagnosis target in the set of electrochemical parameters is the solution resistance; or determining that a target electrochemical parameter corresponding to the diagnostic target in the set of electrochemical parameters is the diffusion impedance coefficient; The diagnostic unit 203 is specifically configured to: determining a diagnosis result of the electrolytic tank according to a difference between the solution resistance at the i+1th moment and the solution resistance at the ith moment; wherein, an abnormal increase in the solution resistance is used to indicate that the diaphragm gap is blocked, the ion is adsorbed, or the electrolyte concentration is changed; or, determining a diagnosis result of the electrolytic tank according to a difference between the diffusion impedance coefficient at the i+1th moment and the diffusion impedance coefficient at the ith moment; wherein, an increase in the diffusion impedance coefficient is used to indicate that the diffusion resistance of the ion in the diaphragm channel is increased.
[0091] Optionally, the device 200 further comprises a model diagnosis unit, configured to: obtain a diagnosis model, wherein the diagnosis model is obtained based on different types of electrochemical parameter samples and diagnosis result labels at different moments; input the set of electrochemical parameters at the i+1th moment and the set of electrochemical parameters at the ith moment into the diagnosis model to obtain the diagnosis result of the electrolytic tank.
[0092] Optionally, the device 200 further comprises a life diagnosis unit, configured to: obtain a standard set of electrochemical parameters, wherein the standard set of electrochemical parameters comprises a plurality of standard electrochemical parameters used to represent a normal operating condition of the electrolytic tank; determine health state information of a target component set in the electrolytic tank according to a difference between the set of electrochemical parameters at the i+1th moment and the standard set of electrochemical parameters, wherein the target component set comprises at least one component, and a difference between the electrochemical parameter of the at least one component and a corresponding standard electrochemical parameter is greater than a difference threshold; determine a life diagnosis result of the electrolytic tank according to the health state information of the target component set.
[0093] Referring to Figure 3 The embodiments of the present application also provide a controller, the controller comprising a memory 301 and a processor 302: The memory is configured to store a computer program and transmit the computer program to the processor; The processor is configured to execute the method of the above-mentioned method embodiments according to the computer program.
[0094] The embodiments of the present application also provide a computer readable storage medium, characterized in that the computer readable storage medium is configured to store a computer program, and the computer program is configured to execute the method of the above-mentioned method embodiments.
[0095] The embodiment of the present application further provides a computer program product including a computer program, which, when running on a computer device, enables the computer device to execute the method of the method embodiment.
[0096] It should be noted that the embodiments in the specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts of each embodiment can be referred to each other.
[0097] The term "comprising" and its variants, as used in the specification, are open-ended, i.e., "including but not limited to". The term "based on" is "at least partially based on". The term "one embodiment" means "at least one embodiment"; the term "another embodiment" means "at least one additional embodiment"; the term "some embodiments" means "at least some embodiments". Related definitions of other terms will be given in the following description.
[0098] It should be understood that in the present application, "at least one" means one or more, and "multiple" means two or more. "And / or", used to describe the association between the associated objects, means that there can be three relationships, for example, "A and / or B" can mean: only A, only B, and A and B exist at the same time, where A and B can be singular or plural. The character " / " generally represents an "or" relationship between the associated objects. "At least one of the following" or similar expressions means any combination of these items, including single item or any combination of multiple items. For example, at least one of a, b or c, can mean: a, b, c, "a and b", "a and c", "b and c", or "a and b and c", where a, b, c can be single or multiple.
[0099] It should also be noted that in this paper, relationship terms such as first and second are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between the entities or operations. Moreover, the terms "include", "contain" or any other variant thereof are intended to cover non-exclusive inclusion, so that the process, method, article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed or inherent to such process, method, article or device. Without more limitations, the element defined by the sentence "including a…" does not exclude the existence of other identical elements in the process, method, article or device including the element.
[0100] The steps of a method or algorithm described in connection with the embodiments disclosed herein can be embodied directly in hardware, in a software module executed by a processor, or in a combination of the two. A software module can reside in RAM, flash memory, ROM, electrically programmable ROM (EPROM), electrically erasable programmable ROM (EEPROM), registers, hard disk, a removable disk, a CD-ROM, or any other form of storage medium known in the art. The exemplary storage media are coupled to the processor such the processor can read information from, and write information to, the storage media.
[0101] The above description of disclosed embodiments is intended to be illustrative and not restrictive. Many embodiments of the application will be apparent to those of skill in the art upon reviewing the above description. The scope of the application should, therefore, be determined not with reference to the above description, but instead with reference to the appended claims, along with their full scope of equivalents.
Claims
1. A method of diagnosing an electrolytic cell, characterized by, The method comprises: driving an alternating excitation signal to be superimposed on an electrolytic cell, based on a sampling time sequence corresponding to the alternating excitation signal, acquiring a voltage sequence at the i+1 moment and a current sequence at the i+1 moment of the electrolytic cell, i being a positive integer; determining impedance data of the electrolytic cell at the i+1 moment according to the voltage sequence at the i+1 moment and the current sequence at the i+1 moment; determining an electrochemical parameter set at the i+1 moment according to the impedance data at the i+1 moment, the electrochemical parameters in the electrochemical parameter set being used to characterize the electrochemical process of the electrolytic cell; determining a diagnosis result of the electrolytic cell according to the difference between the electrochemical parameter set at the i+1 moment and the electrochemical parameter set at the i moment.
2. The method of claim 1, wherein, The voltage sequence comprises a plurality of frequency sub-voltage sequences, and the current sequence comprises a plurality of frequency sub-current sequences. The determination of the impedance data of the electrolytic cell at the i+1 moment according to the voltage sequence at the i+1 moment and the current sequence at the i+1 moment comprises: for the i+1 moment, acquiring a target frequency sub-voltage sequence and a target frequency sub-current sequence, the target frequency being one of the plurality of frequencies; generating a reference signal corresponding to the alternating excitation signal based on the target frequency; performing correlation operation on the target frequency sub-voltage sequence and the reference signal to obtain a target frequency voltage correlation result, and performing correlation operation on the target frequency sub-current sequence and the reference signal to obtain a target frequency current correlation result; determining the target frequency impedance data according to the target frequency voltage correlation result and the target frequency current correlation result; taking each frequency as the target frequency respectively to obtain the impedance data of the electrolytic cell at the i+1 moment.
3. The method of claim 1, wherein, The determination of the electrochemical parameter set at the i+1 moment according to the impedance data at the i+1 moment comprises: acquiring a plurality of initial electrochemical parameters, the initial electrochemical parameters being electrochemical parameters that have not been fitted numerically; performing fitting on the plurality of initial electrochemical parameters according to the impedance data at the i+1 moment to obtain the electrochemical parameter set at the i+1 moment.
4. The method of claim 1, wherein, The determination of the diagnosis result of the electrolytic cell according to the difference between the electrochemical parameter set at the i+1 moment and the electrochemical parameter set at the i moment comprises: acquiring a diagnosis target; determining a target electrochemical parameter corresponding to the diagnosis target in the electrochemical parameter set; determining the diagnosis result of the electrolytic cell according to the difference between the target electrochemical parameter at the i+1 moment and the target electrochemical parameter at the i moment.
5. The method of claim 4, wherein, The electrochemical parameters in the electrochemical parameter set include at least one of solution resistance, charge transfer resistance, amplitude parameter of constant phase element, index parameter of constant phase element, and diffusion impedance coefficient.
6. The method of claim 5, wherein, If the diagnosis target is used to diagnose the attenuation of the catalyst, the determination of the target electrochemical parameter corresponding to the diagnosis target in the electrochemical parameter set comprises: determining the target electrochemical parameter corresponding to the diagnosis target in the set of electrochemical parameters as the charge transfer resistance; the diagnosis result of the electrolytic cell is determined according to the difference between the target electrochemical parameter at the i+1 moment and the target electrochemical parameter at the i moment, including: the diagnosis result of the electrolytic cell is determined according to the difference between the charge transfer resistance at the i+1 moment and the charge transfer resistance at the i moment; wherein, the increase of the charge transfer resistance indicates the decrease of the activity of the catalyst; if the diagnosis target is used to diagnose the diaphragm, the determination of the target electrochemical parameter corresponding to the diagnosis target in the set of electrochemical parameters as the charge transfer resistance includes: determining the target electrochemical parameter corresponding to the diagnosis target in the set of electrochemical parameters as the solution resistance; or, determining the target electrochemical parameter corresponding to the diagnosis target in the set of electrochemical parameters as the diffusion impedance coefficient; the diagnosis result of the electrolytic cell is determined according to the difference between the target electrochemical parameter at the i+1 moment and the target electrochemical parameter at the i moment, including: the diagnosis result of the electrolytic cell is determined according to the difference between the solution resistance at the i+1 moment and the solution resistance at the i moment; wherein, the abnormal increase of the solution resistance indicates the blockage of the diaphragm gap, the adsorption of contaminated ions or the change of the electrolyte concentration; or, the diagnosis result of the electrolytic cell is determined according to the difference between the diffusion impedance coefficient at the i+1 moment and the diffusion impedance coefficient at the i moment; wherein, the increase of the diffusion impedance coefficient indicates the increase of the diffusion resistance of ions in the diaphragm channel.
7. The method of claim 1, wherein, The method further includes: obtaining a diagnosis model, the diagnosis model being trained based on different types of electrochemical parameter samples and diagnosis result labels at different moments; inputting the set of electrochemical parameters at the i+1 moment and the set of electrochemical parameters at the i moment into the diagnosis model to obtain the diagnosis result of the electrolytic cell.
8. The method of claim 1, wherein, The method further includes: obtaining a standard set of electrochemical parameters, the standard set of electrochemical parameters including a plurality of standard electrochemical parameters for characterizing the normal operating condition of the electrolytic cell; determining the health state information of a target component set in the electrolytic cell according to the difference between the set of electrochemical parameters at the i+1 moment and the standard set of electrochemical parameters, the target component set including at least one component, and the difference between the electrochemical parameter of the at least one component and the corresponding standard electrochemical parameter being greater than a difference threshold; determining the life diagnosis result of the electrolytic cell according to the health state information of the target component set.
9. An electrolyzer diagnostic device, characterized by The device includes: an excitation unit configured to drive an alternating current excitation signal superimposed on the electrolytic cell, and obtain a voltage sequence at an i+1 moment and a current sequence at an i+1 moment of the electrolytic cell based on a sampling time sequence corresponding to the alternating current excitation signal, i being a positive integer; a determination unit configured to determine impedance data of the electrolytic cell at the i+1 moment according to the voltage sequence at the i+1 moment and the current sequence at the i+1 moment. The determining unit is configured to determine, according to the impedance data at the i+1th moment, an electrochemical parameter set at the i+1th moment, the electrochemical parameter set including electrochemical parameters for characterizing an electrochemical process of the electrolytic cell; The diagnosing unit is configured to determine a diagnosis result of the electrolytic cell according to a difference between the electrochemical parameter set at the i+1th moment and the electrochemical parameter set at the ith moment.
10. A controller characterized by comprising: The controller includes a processor and a memory: The memory is configured to store a computer program and transmit the computer program to the processor; The processor is configured to execute the method according to any one of claims 1-8 according to the computer program.