Maintenance system and method for zinc-bromine flow battery electrolyte

Abstract

The invention provides a maintenance system and method for a zinc-bromine flow battery electrolyte, and the system comprises a detection module which obtains the information of the electrolyte in a liquid storage tank based on a first control signal transmitted by a blending module; the blending module obtains and analyzes the electrolyte information in the zinc-bromine flow battery collected by the detection module, and generates a blending signal based on an analysis result obtained through analysis; the liquid supplementing module is used for supplementing the electrolyte in the liquid storage tank through the blending signal; and the maintenance module is used for cleaning sediments on an electrode in the liquid storage tank and filtering electrolyte in the liquid storage tank through the allocation signal. According to the system, the electrolyte state is monitored in real time through the detection module; the blending module accurately analyzes and generates a blending signal; the electrolyte supplementing module timely supplements the electrolyte to maintain stable performance; the maintenance module effectively cleans electrode deposits and filters the electrolyte, so that the battery is always in the optimal working state, the battery performance is remarkably improved, and the service life is prolonged; meanwhile, the safety is improved, and the maintenance cost is reduced.

Description

Technical Field

[0001] The present invention belongs to the technical field of flow battery maintenance, and more particularly to a maintenance system and method for the electrolyte of a zinc-bromine flow battery. Background Art

[0002] As an advanced electrochemical energy storage technology, the zinc-bromine flow battery (Zn-Br Flow Battery) has unique advantages in its high energy density (up to 70 - 85 Wh / kg). This characteristic enables the zinc-bromine flow battery to store more electrical energy under the same weight or volume, thus meeting the requirements of large-scale energy storage systems, which is of great significance for application scenarios such as power system peak shaving, valley filling, standby power supply, and grid connection of renewable energy. In addition to high energy density, the zinc-bromine flow battery also has the advantage of low cost. Its main raw materials, zinc and bromine, are relatively abundant and low-cost elements, which gives the zinc-bromine flow battery greater competitiveness in manufacturing cost. At the same time, the long cycle potential of the zinc-bromine flow battery is also one of the reasons for its attention. Compared with some other types of batteries, the zinc-bromine flow battery can withstand more charge-discharge cycles, thereby extending the battery life and reducing the overall cost of the energy storage system.

[0003] However, the electrolyte of the zinc-bromine flow battery is usually an acidic solution of ZnBr2 and HBr. During the long-term operation of the battery, zinc ions (Zn 2+ ) and bromide ions (Br - ) have a concentration gradient due to differences in deposition and dissolution rates during the charge-discharge process, leading to polarization effects and reduced energy efficiency. Also, during use, uneven zinc deposition on the negative electrode easily forms dendrites, piercing the diaphragm, resulting in a short circuit problem in the battery. At the same time, the permeability and volatility of bromine (Br2) lead to increased self-discharge, corroding the seals at the connection positions between the liquid storage tank for storing the electrolyte and other components in the battery, causing electrolyte leakage;

[0004] Regarding the problems existing in the zinc-bromine flow battery, the prior art often deals with them through manual detection methods, that is, by regularly shutting down the machine, the detection personnel collect the information of the electrolyte through a sampler, and according to the collected information, manually supplement the electrolyte. During the collection process, when it is found that there are many impurities in the electrolyte, the electrolyte is manually filtered through a filter. Although the maintenance of the electrolyte in the zinc-bromine flow battery can be completed manually, it is necessary to regularly maintain the electrolyte in the zinc-bromine flow battery, which is time-consuming and laborious. And when the electrolyte consumption in the battery is too large, the regular detection and maintenance cannot timely supplement the electrolyte, resulting in the battery being in a low energy storage state and affecting the working efficiency of the equipment where it is located. Summary of the Invention

[0005] To solve the problems that the existing zinc-bromine flow battery requires time-consuming and laborious manual inspection and maintenance, and during the use of the zinc-bromine flow battery, the consumed electrolyte cannot be replenished in time, resulting in the zinc-bromine flow battery being in a low energy storage state, the present invention provides a maintenance system and method for the electrolyte of a zinc-bromine flow battery.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention proposes a maintenance system for the electrolyte of a zinc-bromine flow battery, and the system includes:

[0008] A detection module: used to obtain the electrolyte information in the liquid storage tank based on the first control signal transmitted by the preparation module;

[0009] A preparation module: used to obtain the electrolyte information in the zinc-bromine flow battery collected by the detection module, analyze it, and generate a preparation signal based on the analysis result;

[0010] A liquid replenishment module: used to replenish the electrolyte in the liquid storage tank through the preparation signal;

[0011] A maintenance module: used to clean the deposits on the electrodes in the liquid storage tank and filter the electrolyte in the liquid storage tank through the preparation signal.

[0012] Preferably, the detection module includes a collection unit and a first processing unit;

[0013] The collection unit includes an ion-selective electrode, a discharge times collector, an ultraviolet-visible spectroscopy probe, an electrochemical detector, and a viscosity sensor;

[0014] The ion-selective electrode, the ultraviolet-visible spectroscopy probe, the electrochemical detector, and the viscosity sensor are all integrated in the liquid storage tank inside the zinc-bromine flow battery;

[0015] The ion-selective electrode is used to collect the Zn 2+ concentration data and Br - concentration data in the electrolyte in the liquid storage tank in real time;

[0016] The ultraviolet-visible spectroscopy probe is used to collect the Br2 content data and Br3 - content data in the electrolyte in the liquid storage tank in real time;

[0017] The electrochemical detector is used to measure the redox potential data and pH value occurring in the electrolyte in the liquid storage tank in real time;

[0018] The discharge times collector is used to detect the discharge times of the zinc-bromine flow battery;

[0019] The viscosity sensor is used to detect the electrolyte viscosity data in the liquid storage tank in real time.

[0020] Preferably, the first processing unit includes a data screening and processing sub-unit, a data anomaly division sub-unit, and a data storage sub-unit;

[0021] The data screening and processing sub-unit is used to screen and process the collected electrolyte information and mark the abnormal data in the electrolyte information;

[0022] The data anomaly division sub-unit is used to extract the abnormal data from the marked electrolyte information, assign a unique anomaly code to the abnormal data, associate the pre-stored tag information therein with the anomaly code, and then transmit the associated electrolyte information to the data storage sub-unit for storage.

[0023] Preferably, the dispensing module includes a data acquisition unit, a central processing unit, a compensation amount calculation unit, a storage unit, and an output unit;

[0024] The data acquisition unit is used to acquire the electrolyte information, anomaly code, and the tag information associated with the anomaly code stored in the data storage sub-unit;

[0025] The central processing unit is used to analyze the electrolyte information data acquired by the data acquisition unit and generate a dispensing signal;

[0026] The compensation amount calculation unit is used to calculate compensation data based on the electrolyte information, associate the compensation data with the dispensing signal, and then store and transmit it to the storage unit and the output unit;

[0027] The output unit is used to output the compensation data and the associated dispensing signal.

[0028] Preferably, the liquid replenishment module includes a liquid storage unit, a mixing unit, a metering unit, and a regulation unit;

[0029] Among them, after the regulation unit receives the dispensing signal, it dispenses the compensation liquid in the liquid storage unit to the metering unit. The metering unit measures the corresponding compensation liquid based on the compensation data, inputs it into the mixing unit for mixing, and then inputs it into the liquid storage tank in the zinc-bromine flow battery.

[0030] Preferably, the maintenance module includes a maintenance unit, a filtering unit, a pulsed voltage application unit, and a deposition processing unit;

[0031] The maintenance unit is used to compare the number of discharges with a preset discharge threshold to generate a maintenance processing signal;

[0032] The deposition processing unit is used to release current after receiving the maintenance processing signal to uniformly dissolve the deposits on the electrode;

[0033] The pulse voltage application unit is configured to apply a reverse pulse voltage after receiving a maintenance processing signal;

[0034] The filtering unit is configured to filter the electrolyte after receiving a maintenance processing signal.

[0035] Preferably, the maintenance module further includes an electrodialysis unit;

[0036] The electrodialysis unit is configured to obtain the Br3 content data collected by the ultraviolet-visible spectroscopy probe, and process Br3 based on the Br3 content data; - content data, based on the Br3 - content data process Br3 - .

[0037] Preferably, the system further includes a safety protection module, and the safety protection module includes a bromine leakage treatment unit, a nitrogen purge unit, a safety level prediction unit, and a neutralizing agent spraying unit;

[0038] The bromine leakage treatment unit is connected through a data wire to obtain the ultraviolet-visible spectroscopy probe, and is configured to obtain the Br2 content data collected by the ultraviolet-visible spectroscopy probe;

[0039] The safety level prediction unit is configured to generate an emergency protection signal by processing the Br2 content data;

[0040] The nitrogen purge unit is configured to inject nitrogen into the storage tank in the zinc-bromine flow battery to isolate oxygen after receiving the emergency protection signal;

[0041] The neutralizing agent spraying unit is configured to spray sodium thiosulfate in the zinc-bromine flow battery to neutralize the leaked Br2 after receiving the emergency protection signal.

[0042] The present invention provides a method for maintaining the electrolyte of a zinc-bromine flow battery, which is applied to the above-mentioned maintenance system for the electrolyte of a zinc-bromine flow battery, and includes the following steps:

[0043] The detection module obtains the electrolyte information in the storage tank through the first control signal transmitted by the dispensing module;

[0044] The dispensing module analyzes the electrolyte information in the zinc-bromine flow battery and generates a dispensing signal based on the analysis result;

[0045] The liquid replenishment module replenishes the electrolyte in the storage tank through the dispensing signal, and the maintenance module cleans the deposits on the electrodes in the storage tank and filters the electrolyte in the storage tank through the dispensing signal.

[0046] Compared with the prior art, the present invention has the following beneficial technical effects:

[0047] The present invention provides a maintenance system for the electrolyte of a zinc-bromine flow battery. In this system, the detection module can, based on the control signal of the formulation module, obtain the key information of the electrolyte in the storage tank in real time, ensuring that the electrolyte is always in the best working state and avoiding the decline in battery performance caused by poor electrolyte conditions. The formulation module can quickly generate a reasonable formulation signal by analyzing the data collected by the detection module, guiding the liquid replenishment module to accurately replenish the electrolyte, ensuring that the composition and ratio of the electrolyte always meet the requirements of battery operation, thereby effectively extending the service life of the battery. The liquid replenishment module replenishes the electrolyte in the storage tank in a timely manner according to the formulation signal, avoiding the decline in battery performance caused by insufficient electrolyte, making the concentration deviation of Zn 2+ / Br - within ±3%, and the battery energy efficiency is increased to 78%-82%, enabling the battery to continuously and stably output electrical energy, improving the energy utilization efficiency. The maintenance module cleans the deposits on the electrodes in the storage tank through the formulation signal and filters the electrolyte, effectively removing the impurities and harmful substances generated during the battery operation, reducing the zinc dendrite growth rate by 85%, achieving a cycle life of 6000 times, improving the battery performance and life, and reducing the maintenance cost.

[0048] Furthermore, in this system, the detection module realizes the comprehensive, real-time, and accurate collection and processing of electrolyte information through a highly integrated acquisition unit and a finely processed first processing unit, greatly improving the efficiency and accuracy of electrolyte detection; the acquisition unit integrates an ion-selective electrode, an ultraviolet-visible spectroscopy probe, an electrochemical detector, and a viscosity sensor. These high-precision sensors are respectively responsible for real-time collecting the key parameters such as the Zn 2+ concentration, Br - concentration, Br2 content, Br3 - content, redox potential, pH value, and viscosity in the electrolyte, providing detailed data support for subsequent electrolyte formulation and maintenance, ensuring the accurate monitoring of the electrolyte state; the first processing unit preliminarily screens the collected electrolyte information through the data screening and processing subunit, effectively marking the abnormal data, providing a clear data basis for subsequent processing. The data anomaly division subunit further processes the abnormal data, assigns it a unique anomaly code, and associates it with the pre-stored label information, realizing the rapid identification and classification of abnormal data. Finally, the data storage subunit stores the processed electrolyte information properly, ensuring the integrity and traceability of the data; by the detection module, the accuracy and timeliness of electrolyte detection are improved, the influence of human factors on the detection results is effectively reduced, which helps to extend the service life of the battery, improve the performance stability of the battery, and also reduce the maintenance cost and improve the energy utilization efficiency.

[0049] Furthermore, in this system, the dispensing module works in coordination with a data acquisition unit, a central processing unit, a compensation amount calculation unit, a storage unit, and an output unit to achieve comprehensive acquisition and accurate analysis of electrolyte information. The data acquisition unit extracts electrolyte information, anomaly codes, and their associated tags from the data storage subunit, providing a solid foundation for subsequent dispensing work. The central processing unit then deeply analyzes this information to generate accurate dispensing signals, ensuring that the composition and concentration of the electrolyte are always in an optimal state. The compensation amount calculation unit calculates the required compensation data based on the electrolyte information, associates it with the dispensing signal, and stores it in the storage unit. At the same time, the compensation data and the dispensing signal are transmitted to the liquid replenishment module through the output unit to guide precise liquid replenishment operations.

[0050] Furthermore, in this system, the liquid replenishment module realizes timely replenishment and uniform mixing of the electrolyte through the close cooperation of a liquid storage unit, a mixing unit, a metering unit, and a regulation unit. The regulation unit precisely dispenses the compensation liquid in the liquid storage unit to the metering unit according to the dispensing signal. The metering unit then accurately measures the required amount of compensation liquid based on the compensation data. The compensation liquid is input into the mixing unit to be fully mixed with the electrolyte to ensure the uniformity of the electrolyte composition. The mixed electrolyte is input into the liquid storage tank in the zinc-bromine flow battery to provide a continuous and stable power output for the battery.

[0051] Furthermore, in this system, the maintenance module effectively maintains the zinc-bromine flow battery through the collaborative action of a discharge detection unit, a maintenance unit, a filtration unit, a pulsed voltage application unit, and a deposition processing unit. The discharge detection unit monitors the discharge times of the battery in real time, providing accurate data support for the maintenance unit. The maintenance unit compares the discharge times with a preset discharge threshold and generates a maintenance processing signal when the threshold is reached or exceeded. The deposition processing unit releases current after receiving the maintenance processing signal to uniformly dissolve the deposits on the electrodes, improving the battery efficiency. The pulsed voltage application unit applies a reverse pulsed voltage to further improve the electrode state and extend the battery life. The filtration unit filters the electrolyte to remove impurities and precipitates, maintaining the cleanliness of the electrolyte.

[0052] Furthermore, the maintenance module in this system is also equipped with an electrodialysis unit, which accurately monitors and processes the content of Br3 in the electrolyte by obtaining the Br3 content data collected by an ultraviolet-visible spectroscopy probe. The electrodialysis unit processes the electrolyte based on the Br3 content data to optimize the electrolyte composition and improve the performance and stability of the battery. - content data, and precisely monitors and processes the Br3 content in the electrolyte. - content in the electrolyte. - Based on the Br3 content data, the electrodialysis unit processes the electrolyte to optimize the electrolyte composition and improve the performance and stability of the battery.

[0053] Furthermore, the safety protection module in this system integrates a bromine leakage treatment unit, a nitrogen purging unit, a safety level prediction unit, and a neutralizing agent spraying unit. These units work together to effectively address potential safety risks such as bromine leakage. The bromine leakage treatment unit monitors the Br2 content in the electrolyte in real time. The safety level prediction unit quickly judges the safety status based on the monitoring data and generates an emergency protection signal. Once a bromine leakage risk is detected, the nitrogen purging unit immediately injects nitrogen into the liquid storage tank to effectively isolate oxygen and prevent an explosion caused by the reaction of bromine with oxygen. At the same time, the neutralizing agent spraying unit quickly sprays sodium thiosulfate to neutralize the leaked bromine, further reducing the safety risk, effectively preventing the occurrence of safety accidents, and ensuring the safety of equipment and personnel, providing a solid guarantee for the stable operation of the zinc-bromine flow battery. Description of the Drawings

[0054] Figure 1 It is a system block diagram of a maintenance system for the electrolyte of a zinc-bromine flow battery proposed by the present invention. Detailed Embodiments

[0055] In the following text, only some exemplary embodiments are simply described. As those skilled in the art can recognize, the described embodiments can be modified in various different ways without departing from the spirit or scope of the present invention. Therefore, the drawings and the description are considered to be exemplary in nature rather than restrictive.

[0056] In the description of the present invention, it should be understood that the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings. It is only for the convenience of describing the present invention and simplifying the description, and does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus cannot be understood as a limitation of the present invention.

[0057] In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include one or more of such features. In the description of the present invention, "a plurality" means two or more unless otherwise specifically defined.

[0058] In the present invention, unless otherwise clearly specified or limited, terms such as "installation", "connection", "linkage", "fixation" shall be understood in a broad sense. For example, it may be a fixed connection, a detachable connection, or an integral body; it may be a mechanical connection, an electrical connection, or a communication connection; it may be a direct connection or an indirect connection through an intermediate medium, and it may be the internal communication between two components or the interaction relationship between two components. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0059] In the present invention, unless otherwise clearly specified or limited, the first feature being "above" or "below" the second feature may include direct contact between the first and second features, or may include the situation where the first and second features are not in direct contact but in contact through other features therebetween. Moreover, the first feature being "above", "over" and "on top of" the second feature includes the first feature being directly above and obliquely above the second feature, or merely indicating that the horizontal height of the first feature is higher than that of the second feature. The first feature being "below", "beneath" and "underneath" the second feature includes the first feature being directly below and obliquely below the second feature, or merely indicating that the horizontal height of the first feature is lower than that of the second feature.

[0060] The embodiments of the present invention will be described in detail below with reference to the accompanying drawings.

[0061] The zinc-bromine flow battery is regarded as an important technology for large-scale energy storage due to its high energy density (up to 70 - 85 Wh / kg), low cost, and long cycle potential. However, for the electrolyte (usually an acidic solution of ZnBr2 and HBr) in the zinc-bromine flow battery, during long-term use, the stored electrolyte in it will be depleted. Currently, manual replenishment and maintenance of the electrolyte are carried out, resulting in the problem that when the electrolyte is lacking during the use of the zinc-bromine flow battery, the electrolyte cannot be replenished in a timely manner, affecting the energy storage state of the zinc-bromine flow battery.

[0062] In view of the problems existing in the maintenance process of the above zinc-bromine flow battery, the present invention proposes a maintenance system for the electrolyte of a zinc-bromine flow battery. This system includes a formulation module, a detection module, a liquid replenishment module, and a maintenance module. Among them, the detection module is installed in the liquid storage tank of the zinc-bromine flow battery and is used to obtain the electrolyte information in the liquid storage tank based on the first control signal transmitted by the formulation module. The formulation module is connected to the detection module, the liquid replenishment module, and the maintenance module through data wires, and is used to obtain the electrolyte information in the zinc-bromine flow battery collected by the detection module, analyze it, and generate a formulation signal based on the analysis result. The liquid replenishment module is used to replenish the electrolyte in the liquid storage tank according to the formulation signal. The maintenance module is used to clean the zinc dendrites on the electrodes in the liquid storage tank and filter the electrolyte in the liquid storage tank according to the formulation signal.

[0063] The detection module includes a collection unit and a first processing unit. The first processing unit is connected to the dispensing module and the collection unit through a data wire, and is used to process the electrolyte information collected by the collection unit and transmit it to the dispensing module. The collection unit includes ion-selective electrodes, a discharge times detector, an ultraviolet-visible spectroscopy probe (UV-Vis), an electrochemical detector, and a viscosity sensor. A plurality of ion-selective electrodes, ultraviolet-visible spectroscopy probes (UV-Vis), electrochemical detectors, and viscosity sensors are provided. The ion-selective electrodes, ultraviolet-visible spectroscopy probes (UV-Vis), electrochemical detectors, and viscosity sensors are all integrated in the liquid storage tank. The ion-selective electrodes, ultraviolet-visible spectroscopy probes (UV-Vis), electrochemical detectors, and viscosity sensors are all connected to the first processing unit through data wires. Among them, the ion-selective electrode is used to collect the Zn 2+ concentration data and Br- concentration data in the electrolyte in the liquid storage tank in real time, and the detection accuracy range is -0.05M to 0.05M; the ultraviolet-visible spectroscopy probe is used to collect the Br2 content data and Br3 - content data in the electrolyte in the liquid storage tank in real time. The wavelength range of the ultraviolet-visible spectroscopy probe is 250 to 600nm; the electrochemical detector is used to measure the redox potential data and pH value occurring in the electrolyte in the liquid storage tank in real time; the viscosity sensor is used to detect the electrolyte viscosity data in the liquid storage tank in real time; the discharge times detector is arranged on the electrode of the zinc-bromine flow battery. The discharge times detector is connected to the maintenance module through a data wire and is used to detect the discharge times of the zinc-bromine flow battery and transmit the discharge times to the maintenance module.

[0064] The first processing unit includes a data screening and processing sub-unit, a data anomaly division sub-unit, and a data storage sub-unit. Among them, the data screening and processing sub-unit is connected to the ion-selective electrode, the ultraviolet-visible spectroscopy probe (UV-Vis), the data anomaly division sub-unit, the electrochemical detector, and the viscosity sensor through a data wire, and is used to screen and process the collected electrolyte information and mark the abnormal data in the electrolyte information. Exemplarily, the data screening and processing sub-unit screens the Zn2+ concentration data and Br - concentration data collected by the ion-selective electrode, and extracts the Zn 2+ concentration data and Br - abnormal data in the concentration data, that is, compares all the Zn 2+ concentration data collected by the ion-selective electrodes to determine the data in the Zn 2+ concentration data that differs from other data by more than one order of magnitude. In the present invention, one order of magnitude is defined as 2, that is, all Zn 2+Compare every two data in the concentration data to obtain the data difference. If the difference between one data and other data is 2, then extract this data and mark it as abnormal data. Based on the above principle, complete the screening process for the Br - concentration data, Br2 content data, Br3 - content data, redox potential data, pH data, and electrolyte viscosity data, and transfer the processed data to the data anomaly division sub-unit.

[0065] The data anomaly division sub-unit is connected to the data storage sub-unit through a data wire. The data storage sub-unit is connected to the dispensing module through a data wire. After receiving the marked electrolyte information, it extracts the abnormal data, assigns a unique anomaly code to the abnormal data, associates the pre-stored label information in it with the anomaly code, and then transfers the associated electrolyte information to the data storage sub-unit for storage. Among them, the label information includes the data type and the reason corresponding to the occurrence of the abnormal data.

[0066] The dispensing module includes a data acquisition unit, a central processing unit, a compensation amount calculation unit, a storage unit, and an output unit;

[0067] The data acquisition unit is connected to the data storage sub-unit through a data wire, and is used to obtain the electrolyte information, anomaly code, and label information associated with the anomaly code stored in the data storage sub-unit, and transfer these data to the central processing unit for processing;

[0068] The central processing unit is used to analyze the electrolyte information data, generate a dispensing signal, and transfer the dispensing signal to the compensation amount calculation unit and the output unit. Exemplarily, calculate the concentration difference between the Zn2+ concentration data and the Br - concentration data in the electrolyte information, compare the concentration difference with a preset concentration value. If the concentration difference is greater than the preset first concentration threshold (0.3M), generate a first dispensing signal. When the concentration difference is less than the preset second concentration threshold (-0.3M), generate a second dispensing signal. If the concentration difference is between the first concentration threshold and the second concentration threshold, then compare the Zn 2+ concentration data with the preset first threshold (1.2M). When the Zn 2+ concentration data is less than the first gradient threshold (1.2M), generate a third dispensing signal; compare the Br2 content data in the electrolyte information with the preset second threshold (0.1M). If the Br2 content data is greater than the second threshold (0.1M), generate a fourth dispensing signal; compare the electrolyte viscosity data with the third threshold (15cP). If the electrolyte viscosity data is greater than the third threshold (15cP), generate a fifth dispensing signal and associate it with the first dispensing signal;

[0069] The compensation amount calculation unit is connected to the storage unit and the output unit through data wires, and is used to calculate compensation data based on the electrolyte information, associate the compensation data with the dispensing signal, store it in the storage unit, and transmit it to the output unit. Exemplarily, the compensation amount calculation unit obtains the concentration difference, and through the principle of charge conservation, calculates the first compensation amount of the hydrobromic acid solution or the first compensation amount of the zinc bromide solution, associates the first compensation amount of the hydrobromic acid solution with the first dispensing signal, and associates the first compensation amount of the zinc bromide solution with the second dispensing signal, and obtains Zn 2+ concentration data, and through the principle of charge conservation, calculates the second compensation amount of the hydrobromic acid solution, and calculates the second compensation amount of the zinc bromide solution according to the molar ratio of Zn 2+ :H + =1:2, associates the second compensation amount of the hydrobromic acid solution and the second compensation amount of the zinc bromide solution with the third dispensing signal; and obtains the Br2 content data collected by the ultraviolet-visible spectroscopy probe processed by the third dispensing signal by the liquid supplement module, and calculates the quaternary ammonium salt solution compensation amount through the principle of mass conservation, and associates the quaternary ammonium salt solution compensation amount with the fourth dispensing signal; calculates the deionized water compensation amount through the obtained electrolyte viscosity data and the electrolyte standard viscosity data, and associates the deionized water compensation amount with the fifth dispensing signal and the associated third dispensing signal, and transmits it to the storage unit for storage and the output unit for transmission.

[0070] The storage unit is used to store the compensation data and the associated dispensing signal. A marking unit is set for each storage subunit in the storage unit, and the marking unit is used to record the storage time when the compensation data and the associated dispensing signal are input into the storage subunit;

[0071] The output unit is connected to the liquid supplement module through a data wire, and transmits the compensation data and the associated dispensing signal to the liquid supplement module.

[0072] The liquid replenishment module includes a liquid storage unit, a mixing unit, a metering unit, and a regulation unit. The regulation unit is connected to the liquid storage unit, the metering unit, and the mixing unit through data wires. Among them, the liquid storage unit is connected to the metering unit through a conduit, the metering unit is connected to the mixing unit through a conduit, and the mixing unit is integrated in the liquid storage tank inside the zinc-bromine flow battery. After receiving the deployment signal, the regulation unit deploys the compensating liquid in the liquid storage unit to the metering unit. The metering unit measures the corresponding compensating liquid based on the compensation data, inputs it to the mixing unit for mixing, and then inputs it to the liquid storage tank inside the zinc-bromine flow battery. Exemplarily, after receiving the first deployment signal, the regulation unit deploys the hydrobromic acid solution in the liquid storage unit to the metering unit. The metering unit measures the corresponding hydrobromic acid solution through the first compensation amount of the hydrobromic acid solution or the first compensation amount of the zinc bromide solution, inputs it to the mixing unit for mixing, and then inputs it to the liquid storage tank inside the zinc-bromine flow battery. After receiving the second deployment signal, the regulation unit deploys the zinc bromide solution in the liquid storage unit to the metering unit. The metering unit measures the corresponding zinc bromide solution through the first compensation amount of the zinc bromide solution, inputs it to the mixing unit for mixing, and then inputs it to the liquid storage tank inside the zinc-bromine flow battery. After receiving the third deployment signal, the regulation unit deploys the zinc bromide solution and the hydrobromic acid solution in the liquid storage unit to the metering unit. The metering unit measures the corresponding zinc bromide solution and hydrobromic acid solution through the second compensation amount of the hydrobromic acid solution and the second compensation amount of the zinc bromide solution, inputs it to the mixing unit for mixing, and then inputs it to the liquid storage tank inside the zinc-bromine flow battery. The compensation call process for the quaternary ammonium salt solution and the ion water compensation amount is the same as above.

[0073] The maintenance module includes a maintenance unit, a filtering unit, a pulsed voltage application unit, and a deposition treatment unit. Among them, the maintenance unit is connected to the deposition treatment unit, the discharge times detector, and the pulsed voltage application unit through data wires, and is used to obtain the discharge times of the bromine flow battery collected by the discharge times detector, and compare the discharge times with a preset discharge threshold. In this embodiment, the preset discharge threshold is 50 times, that is, when the discharge times are greater than 50 times, a maintenance processing signal is generated. The deposition treatment unit is used to release a current of 0.1C after receiving the maintenance processing signal, and uniformly dissolve the deposits on the electrode through the 0.1C current. The pulsed voltage application unit is used to apply a reverse pulsed voltage after receiving the maintenance processing signal. Among them, the amplitude range of the reverse pulsed voltage is -50mV to +50mV, the frequency is 1kHz, the duty cycle is 50%, and it lasts for 10 minutes.

[0074] The filtering unit is connected to the maintenance unit through a data wire, and filters the electrolyte after receiving the maintenance processing signal.

[0075] The maintenance module further includes an electrodialysis unit. The electrodialysis unit is connected to the ultraviolet-visible spectroscopy probe through a data wire and is used to obtain Br3 collected by the ultraviolet-visible spectroscopy probe -Content data, Br3 - Compare the content data with the dialysis threshold. If the Br3 - content data is greater than the dialysis threshold, then at a voltage of 0.5 V, selectively separate Br3 through an anion exchange membrane - and reduce it to Br at the cathode - .

[0076] This system also includes a warning module. The warning module includes an analysis unit, a display and control unit, and a prompt unit. Among them, the analysis unit is connected to the data storage subunit through a data wire, and is used to obtain the abnormal code stored in the data storage subunit, and extract the label information associated with the abnormal code. The analysis unit extracts the pre-stored historical fault data therein based on the type data in the label information, compares the fault determination data in the historical fault data with the abnormal data, determines the abnormal situation that occurs in the zinc-bromine flow battery corresponding to the abnormal data, and extracts the historical solution strategy corresponding to the abnormal situation, and transmits the historical solution strategy to the prompt unit. The prompt unit transmits it to the display and control unit for warning through the display and control unit.

[0077] This system also includes a safety protection module. The safety protection module includes a bromine leakage treatment unit, a nitrogen purging unit, a safety level prediction unit, and a neutralizing agent spraying unit. Among them, the bromine leakage treatment unit is connected to obtain a UV-visible spectroscopy probe through a data wire, and is used to obtain the Br2 content data collected by the UV-visible spectroscopy probe. The safety level prediction unit is connected to the display and control unit, the nitrogen purging unit, and the neutralizing agent spraying unit through a data wire, and is used to obtain the Br2 content data collected by the UV-visible spectroscopy probe, compare the Br2 content data with the emergency threshold (10 ppm), and when the Br2 content data is greater than 10 ppm, generate an emergency protection signal and transmit it to the display and control unit, the nitrogen purging unit, and the neutralizing agent spraying unit. After receiving the emergency protection signal, the nitrogen purging unit injects nitrogen into the liquid storage tank of the zinc-bromine flow battery to isolate oxygen. At the same time, after receiving the emergency protection signal, the neutralizing agent spraying unit sprays sodium thiosulfate to neutralize the leaked Br2 in the zinc-bromine flow battery.

[0078] This system also includes a self-check module. The self-check module is connected to the maintenance module, the warning module, the safety protection module, and the dispensing module through a data wire, and is used to obtain the operating parameters in the maintenance module, the safety protection module, and the dispensing module, compare the operating parameters with the laboratory titration parameters, obtain error data, and if the error data is greater than 5%, then give a warning through the warning module.

[0079] The present invention also proposes a method for maintaining the electrolyte of a zinc-bromine flow battery, which is applied to the above-mentioned maintenance system for the electrolyte of a zinc-bromine flow battery, and specifically includes the following steps:

[0080] The detection module obtains the electrolyte information in the liquid storage tank through the first control signal transmitted by the dispensing module;

[0081] The dispensing module analyzes the electrolyte information in the zinc-bromine flow battery and generates a dispensing signal based on the analysis result obtained;

[0082] The liquid replenishment module replenishes the electrolyte in the liquid storage tank through the dispensing signal, and the maintenance module cleans the deposits on the electrodes in the liquid storage tank and filters the electrolyte in the liquid storage tank through the dispensing signal.

[0083] Specifically, the central processing unit in the dispensing module generates a first control signal through the set detection duration interval therein. The data screening and processing sub-unit in the detection module receives the first control signal and controls the acquisition unit to acquire the electrolyte information in the liquid storage tank of the zinc-bromine flow battery. Among them, the ion-selective electrode real-time collects the Zn 2+ concentration data and Br - concentration data in the electrolyte of the liquid storage tank; the ultraviolet-visible spectroscopy probe real-time collects the Br2 content data and Br3 - content data in the electrolyte of the liquid storage tank, the electrochemical detector real-time measures the redox potential data and pH value occurring in the electrolyte in the liquid storage tank; the viscosity sensor real-time detects the electrolyte viscosity data in the liquid storage tank;

[0084] Transmit the collected electrolyte information to the data screening and processing sub-unit, screen and process the collected electrolyte information, mark the abnormal data in the electrolyte information, then extract the abnormal data in the marked electrolyte information through the data anomaly division sub-unit, assign a unique anomaly code to the abnormal data, and associate the pre-stored tag information therein with the anomaly code, and then transmit the associated electrolyte information to the data storage sub-unit for storage;

[0085] The data acquisition unit acquires the electrolyte information, anomaly code, and tag information associated with the anomaly code stored in the data storage sub-unit. The central processing unit analyzes the electrolyte information data, that is, calculates the concentration difference between the Zn 2+ concentration data and Br - concentration data in the electrolyte information, compares the concentration difference with the preset concentration value. If the concentration difference is greater than the preset first concentration threshold (0.3M), generate a first dispensing signal. When the concentration difference is less than the preset second concentration threshold (-0.3M), generate a second dispensing signal. If the concentration difference is between the first concentration threshold and the second concentration threshold, then compare the Zn2+ concentration data with the preset first threshold (1.2M). When Zn 2+When the concentration data is less than the first gradient threshold (1.2 M), a third formulation signal is generated; the Br2 content data in the electrolyte information is compared with a preset second threshold (0.1 M). If the Br2 content data is greater than the second threshold (0.1 M), a fourth formulation signal is generated; the electrolyte viscosity data is compared with a third threshold (15 cP). If the electrolyte viscosity data is greater than the third threshold (15 cP), a fifth formulation signal is generated and associated with the first formulation signal;

[0086] The compensation amount calculation unit obtains the concentration difference. Through the principle of charge conservation, the first compensation amount of hydrobromic acid solution or the first compensation amount of zinc bromide solution is calculated. The first compensation amount of hydrobromic acid solution is associated with the first formulation signal, and the first compensation amount of zinc bromide solution is associated with the second formulation signal to obtain Zn 2+ concentration data. Through the principle of charge conservation, the second compensation amount of hydrobromic acid solution is calculated, and according to the molar ratio Zn 2+ :H + = 1:2, the second compensation amount of zinc bromide solution is calculated. The second compensation amount of hydrobromic acid solution and the second compensation amount of zinc bromide solution are associated with the third formulation signal; and the Br2 content data collected by the ultraviolet-visible spectroscopy probe after the replenishment module processes the third formulation signal is obtained. Through the principle of mass conservation, the compensation amount of quaternary ammonium salt solution is calculated and associated with the fourth formulation signal; through the obtained electrolyte viscosity data and the standard electrolyte viscosity data, the deionized water compensation amount is calculated and associated with the fifth formulation signal and the associated third formulation signal, and then transmitted to the storage unit for storage and the output unit for transmission; the storage unit stores the compensation data and the associated formulation signals and records the storage time of the input storage subunit;

[0087] After the control unit in the liquid replenishment module receives the dispensing signal, it dispenses the compensating liquid in the dispensing liquid storage unit into the metering unit. The metering unit measures the corresponding compensating liquid based on the compensation data, inputs it into the mixing unit for mixing, and then inputs it into the liquid storage tank in the zinc-bromine flow battery. After the control unit receives the first dispensing signal, it dispenses the hydrobromic acid solution in the dispensing liquid storage unit into the metering unit. The metering unit measures the corresponding hydrobromic acid solution through the first compensation amount of the hydrobromic acid solution or the first compensation amount of the zinc bromide solution, inputs it into the mixing unit for mixing, and then inputs it into the liquid storage tank in the zinc-bromine flow battery. After the control unit receives the second dispensing signal, it dispenses the zinc bromide solution in the dispensing liquid storage unit into the metering unit. The metering unit measures the corresponding zinc bromide solution through the first compensation amount of the zinc bromide solution, inputs it into the mixing unit for mixing, and then inputs it into the liquid storage tank in the zinc-bromine flow battery. After the control unit receives the third dispensing signal, it dispenses the zinc bromide solution and the hydrobromic acid solution in the dispensing liquid storage unit into the metering unit. The metering unit measures the corresponding zinc bromide solution and hydrobromic acid solution through the second compensation amount of the hydrobromic acid solution and the second compensation amount of the zinc bromide solution, inputs it into the mixing unit for mixing, and then inputs it into the liquid storage tank in the zinc-bromine flow battery to maintain the pH at 2.5 - 3.5. The compensation call process for the quaternary ammonium salt solution and the ionized water compensation amount is the same as above.

[0088] After the liquid replenishment is completed, the discharge detection unit in the maintenance module detects the number of discharges of the zinc-bromine flow battery. When the number of discharges is greater than 50 times, a maintenance processing signal is generated. After the deposition processing unit receives the maintenance processing signal, it releases a current of 0.1C to uniformly dissolve the deposits on the electrode through the 0.1C current. At the same time, after the pulsed voltage application unit receives the maintenance processing signal, it applies a reverse pulsed voltage with an amplitude range of -50mV to +50mV, a frequency of 1kHz, and a duty cycle of 50%, and lasts for 10 minutes. And the filtering unit receives the maintenance processing signal to filter the electrolyte.

[0089] During the above processing, the bromine leakage treatment unit in the safety protection module obtains the Br2 content data collected by the ultraviolet-visible spectroscopy probe. When the Br2 content data is greater than 10ppm, an emergency protection signal is generated and transmitted to the display control unit, the nitrogen purge unit, and the neutralizing agent spraying unit. After the nitrogen purge unit receives the emergency protection signal, it injects nitrogen into the liquid storage tank in the zinc-bromine flow battery to isolate oxygen. At the same time, after the neutralizing agent spraying unit receives the emergency protection signal, it sprays sodium thiosulfate into the zinc-bromine flow battery to neutralize the leaked Br2.

[0090] After the data storage subunit in the detection module processes the electrolyte information, the analysis unit obtains the abnormal code stored in the data storage subunit, extracts the label information associated with the abnormal code, extracts the pre-stored historical fault data based on the type data in the label information, compares the fault determination data in the historical fault data with the abnormal data, determines the abnormal situation that occurs in the zinc bromine flow battery corresponding to the abnormal data, extracts the historical solution strategy corresponding to the abnormal situation, transmits the historical solution strategy to the prompt unit, and the prompt unit transmits it to the display and control unit for warning through the display and control unit.

[0091] During the operation of the system, the maintenance module, the warning module, the safety protection module, and the deployment module are connected through data wires to obtain the operating parameters in the maintenance module, the safety protection module, and the deployment module, compare the operating parameters with the laboratory titration parameters to obtain error data. If the error data is greater than 5%, warning is given through the warning module.

[0092] The above has shown and described the basic principles, main features and advantages of the present invention. For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and can be implemented in other specific forms without departing from the spirit or basic features of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be regarded as limiting the claims involved.

[0093] In addition, it should be understood that although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art. The above content is only to illustrate the technical idea of the present invention and cannot be used to limit the protection scope of the present invention. Any modification made on the basis of the technical solution according to the technical idea proposed by the present invention falls within the protection scope of the claims of the present invention.

Claims

1. A maintenance system for zinc-bromine flow battery electrolyte, characterized in that: The system comprises: Detection module: used to obtain electrolyte information in the liquid storage tank based on the first control signal transmitted by the preparation module; The deployment module is used to obtain the electrolyte information in the zinc-bromine flow battery collected by the detection module, analyze it, and generate a deployment signal based on the analysis results; Refilling module: used to replenish the electrolyte in the storage tank by adjusting the signal; Maintenance module: used to clean the deposits on the electrodes in the liquid storage tank and filter the electrolyte in the liquid storage tank by adjusting the signal.

2. A zinc-bromine flow battery electrolyte maintenance system according to claim 1, characterized in that: The detection module includes a collection unit and a first processing unit; The collection unit is used to collect electrolyte information in the liquid storage tank of the zinc-bromine flow battery; The first processing unit is used to process the electrolyte information collected by the collection unit and transmit it to the preparation module.

3. A zinc-bromine flow battery electrolyte maintenance system according to claim 2, characterized in that: The collection unit includes an ion selective electrode, a discharge frequency collector, an ultraviolet-visible spectrum probe, an electrochemical detector and a viscosity sensor; The ion selective electrode, the UV-visible spectrometer probe, the electrochemical detector and the viscosity sensor are all integrated in a liquid storage tank in the zinc-bromine flow battery; The ion selective electrode is used to collect Zn in the electrolyte in the liquid storage tank in real time. 2+ Concentration data and Br - Concentration data; The UV-visible spectrum probe is used to collect real-time Br2 content data and Br3 - Content data; The electrochemical detector is used to measure the redox potential data and pH value occurring in the electrolyte in the liquid storage tank in real time; The discharge times collector is used to detect the discharge times of the zinc-bromine flow battery; The viscosity sensor is used to detect the viscosity data of the electrolyte in the liquid storage tank in real time.

4. A zinc-bromine flow battery electrolyte maintenance system according to claim 2, characterized in that: The first processing unit includes a data screening processing subunit, a data anomaly classification subunit and a data storage subunit; The data screening and processing subunit is used to screen the collected electrolyte information and mark abnormal data in the electrolyte information; The data anomaly classification subunit is used to extract abnormal data from the marked electrolyte information, assign a unique abnormal code to the abnormal data, associate the pre-stored label information with the abnormal code, and then transmit the associated electrolyte information to the data storage subunit for storage.

5. A zinc-bromine flow battery electrolyte maintenance system according to claim 1, characterized in that: The deployment module includes a data acquisition unit, a central processing unit, a compensation amount calculation unit, a storage unit and an output unit; The data acquisition unit is used to acquire the electrolyte information, the abnormality code and the label information associated with the abnormality code stored in the data storage subunit; The central processing unit is used to analyze the electrolyte information data acquired by the data acquisition unit and generate a deployment signal; The compensation amount calculation unit is used to calculate compensation data based on the electrolyte information, and associate the compensation data with the deployment signal and store it in the storage unit and transmit it to the output unit; The output unit is used to output the compensation data and the associated adjustment signal.

6. A zinc-bromine flow battery electrolyte maintenance system according to claim 1, characterized in that: The liquid replenishment module includes a liquid storage unit, a mixing unit, a metering unit and a control unit; Among them, the control unit is used to mix the compensation liquid in the liquid storage unit into the metering unit after receiving the mixing signal. The metering unit measures out the corresponding compensation liquid based on the compensation data, inputs it into the mixing unit for mixing, and then inputs it into the liquid storage tank in the zinc-bromine liquid flow battery.

7. A zinc-bromine flow battery electrolyte maintenance system according to claim 1, characterized in that: The maintenance module includes a maintenance unit, a filtering unit, a pulse voltage applying unit and a deposition processing unit; The maintenance unit is used to compare the number of discharges with a preset discharge threshold and generate a maintenance processing signal; The deposition processing unit is used to release current after receiving the maintenance processing signal to evenly dissolve the deposits on the electrode; The pulse voltage applying unit is used to apply a reverse pulse voltage after receiving the maintenance processing signal; The filtering unit is used to filter the electrolyte upon receiving the maintenance processing signal.

8. A zinc-bromine flow battery electrolyte maintenance system according to claim 7, characterized in that: The maintenance module also includes an electrodialysis unit; The electrodialysis unit is used to obtain the Br3 collected by the UV-visible spectrum probe. - Content data, based on the Br3 - Content data processing Br3 - .

9. A zinc-bromine flow battery electrolyte maintenance system according to claim 1, characterized in that: The system further comprises a safety protection module, which comprises a bromine leakage processing unit, a nitrogen purge unit, a safety level prediction unit and a neutralizer spraying unit; The bromine leakage processing unit is connected to the ultraviolet-visible spectrum probe through a data wire to obtain the Br2 content data collected by the ultraviolet-visible spectrum probe; The safety level prediction unit is used to generate an emergency protection signal by processing the Br2 content data; The nitrogen purge unit is used to inject nitrogen into the liquid storage tank of the zinc-bromine flow battery to isolate oxygen after receiving the emergency protection signal; The neutralizer spraying unit is used to neutralize the leaked Br2 into the sodium thiosulfate of the zinc-bromine flow battery after receiving the emergency protection signal.

10. A method for maintaining a zinc-bromine flow battery electrolyte, using a zinc-bromine flow battery electrolyte maintenance system according to any one of claims 1 to 9, characterized in that: The following steps are involved: The detection module obtains information about the electrolyte in the liquid storage tank through the first control signal transmitted by the preparation module; The deployment module analyzes electrolyte information in the zinc-bromine flow battery and generates a deployment signal based on the analysis results obtained; The replenishment module replenishes the electrolyte in the liquid storage tank through the deployment signal, and the maintenance module cleans the deposits on the electrodes in the liquid storage tank and filters the electrolyte in the liquid storage tank through the deployment signal.

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