Real-time monitoring method and system for hydrogen evolution reaction of flow battery

Abstract

The invention relates to a flow battery hydrogen evolution reaction real-time monitoring method and system, and the method comprises the steps: obtaining real-time data in a battery management system; calculating the hydrogen ion concentration in the positive electrode electrolyte in the flow battery by adopting a simultaneous equation; according to the hydrogen ion concentration in the positive electrode electrolyte, the negative electrode equilibrium mixed potential is calculated by combining the positive electrode equilibrium potential; calculating the equilibrium potential of the negative electrode hydrogen evolution reaction according to the negative electrode equilibrium mixed potential; calculating the hydrogen ion concentration in the negative electrode electrolyte according to the equilibrium potential of the negative electrode hydrogen evolution reaction; calculating the amount of substance of hydrogen ions for hydrogen evolution according to the concentration of the hydrogen ions in the negative electrode electrolyte and a simultaneous equation; the amount of substance in which hydrogen is precipitated is calculated on the basis of the amount of substance of hydrogen ions for hydrogen precipitation. An electrochemical calculation formula is established through BMS real-time data, a gas concentration sensor does not need to monitor the gas phase concentration, the cost is reduced, meanwhile, the system real-time performance is improved, the monitoring result is not influenced by working condition fluctuation, and the data reliability is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of liquid flow batteries, and in particular to a real-time monitoring method and system for hydrogen evolution reaction in liquid flow batteries. Background Art

[0002] In liquid flow batteries, the positive and negative electrodes of all-vanadium liquid flow batteries both use acid solutions containing vanadium ions of different valence states as electrolytes. During the charging process of all-vanadium liquid flow batteries, side reactions will inevitably occur. The capacity loss caused by some side reactions (such as vanadium ion cross-membrane crossing, water volume transfer, etc.) can be restored by simple mixing of liquids; but other side reactions of gas evolution cause Faraday imbalance, which cannot be simply compensated by mixing of liquids. These side reactions will cause the attenuation of coulombic efficiency, voltage efficiency, energy efficiency, and system efficiency, and shorten the life of the liquid flow battery. Therefore, it is particularly necessary to monitor these gas evolution side reactions. Hydrogen, oxygen, and carbon dioxide are the main side reaction gases. Since the equilibrium potential of the hydrogen evolution reaction (0.0Vvs.SHE) is greater than the reduction potential of the negative electrode vanadium ions (-0.255Vvs.SHE), the hydrogen evolution reaction is the most important one.

[0003] At present, hydrogen concentration detection instruments are usually used for preliminary testing. However, these hydrogen concentration detection results are themselves related to the operating conditions of the battery stack (such as operating current density, etc.), and it is necessary to install hydrogen concentration detection instruments and other devices on the battery system, which leads to increased R&D, production and maintenance costs.

[0004] Therefore, it is necessary to provide a new real-time monitoring method for hydrogen evolution reaction in liquid flow batteries. Summary of the invention

[0005] Based on the above problems existing in the prior art, the purpose of the embodiments of the present invention is to provide a real-time monitoring method and system for the hydrogen evolution reaction of a liquid flow battery, by establishing an electrochemical calculation formula through the real-time data of the BMS, without the need for a gas concentration sensor to monitor the gas phase concentration, thereby reducing costs and improving the real-time performance of the system. The monitoring results are not affected by fluctuations in operating conditions, thereby improving data reliability.

[0006] To achieve the above object, the technical solution adopted by the present invention is: a real-time monitoring method for hydrogen evolution reaction in a liquid flow battery, comprising: Get real-time data from the battery management system; The simultaneous equations are used to calculate the hydrogen ion concentration in the positive electrolyte of the flow battery; According to the concentration of hydrogen ions in the positive electrode electrolyte, the negative electrode equilibrium mixed potential is calculated in combination with the positive electrode equilibrium potential; Calculate the equilibrium potential of the negative electrode hydrogen evolution reaction based on the negative electrode equilibrium mixed potential; Calculate the hydrogen ion concentration in the negative electrode electrolyte according to the equilibrium potential of the negative electrode hydrogen evolution reaction; Calculate the amount of hydrogen ion substance used for hydrogen evolution based on the hydrogen ion concentration in the negative electrode electrolyte and the simultaneous equation; The amount of the substance that releases hydrogen is calculated based on the amount of the substance that produces hydrogen ions.

[0007] Furthermore, the real-time data acquisition in the battery management system includes: acquiring the state of charge SOC, open circuit voltage OCV, sampling time, sampling times, acquiring the total amount of vanadium in the positive electrode electrolyte, monitoring the volume of the positive and negative electrode electrolytes respectively, and collecting and calculating the average temperature of the electrolyte in the positive electrode storage tank and the negative electrode storage tank of the liquid flow battery.

[0008] Further, the method of using simultaneous equations to calculate the concentration of hydrogen ions in the positive electrode electrolyte in the flow battery includes: calculating the positive electrode hydrogen ion concentration calculation formula, the amount conservation equation of the positive electrode hydrogen ion, the amount increment calculation formula of the positive electrode hydrogen ion substance caused by the electrochemical reaction and migration, and the positive electrode due to The calculation formula for the amount of hydrogen ion substance increased due to dissociation equilibrium, the positive electrode electrolyte The dissociation equilibrium equation and the positive electrolyte The dissociation rate calculation formula is combined to solve the hydrogen ion concentration in the positive electrode electrolyte.

[0009] Furthermore, the calculation formula for the positive electrode hydrogen ion concentration is:

[0010] in, is the concentration of hydrogen ions in the cathode electrolyte at the time of the i-th sampling, in mol / L; is the amount of hydrogen ions in the positive electrode electrolyte at the time of the i-th sampling, in mol; is the volume of the cathode electrolyte at the i-th sampling, in L; The substance conservation equation of the positive electrode hydrogen ion is:

[0011] in, is the amount of hydrogen ions in the positive electrode electrolyte at the i-1th sampling, in mol; is the amount of hydrogen ions in the positive electrode electrolyte caused by the battery electrochemical reaction and migration during the i-th sampling period, in mol; is the positive electrode electrolyte in the i-th sampling period due to The amount of hydrogen ions increased due to dissociation equilibrium, in mol; The calculation formula for the amount of hydrogen ion substance increment caused by the electrochemical reaction and migration of the positive electrode is:

[0012] in, is the power state of the all-vanadium liquid flow battery at the i-th sampling; is the power state of the all-vanadium liquid flow battery at the i-1th sampling time; is the total vanadium content of the positive electrolyte, in mol; The positive electrode The formula for calculating the amount of hydrogen ion substance increased due to dissociation equilibrium is:

[0013] in, is the electrolyte in the positive electrode at the time of sampling i The dissociation rate is in mol / (L*s); is the time interval of the i-th sampling period, in seconds; The positive electrode electrolyte The dissociation equilibrium equation is:

[0014] in, is the electrolyte in the positive electrode at the time of sampling i The amount of substance in mol; is the electrolyte in the positive electrode at the i-1th sampling The amount of substance in mol.

[0015] The positive electrode electrolyte The dissociation rate calculation formula is:

[0016] in, is the rate parameter, which is 10 mol / (L*s); β is The degree of dissociation was taken as 0.25; is the activity coefficient of hydrogen ions, which is taken as 1; for The activity coefficient is taken as 1.

[0017] Furthermore, the negative electrode equilibrium mixed potential calculation formula is:

[0018] in, is the negative electrode equilibrium mixed potential of the all-vanadium liquid flow battery at the i-th sampling time, in V; is the open circuit voltage of the all-vanadium liquid flow battery at the i-th sampling time, in V; is the positive electrode equilibrium potential of the all-vanadium liquid flow battery at the i-th sampling, in V; The calculation formula for the positive electrode equilibrium potential of all-vanadium liquid flow battery is:

[0019] in, is the standard equilibrium potential of the positive electrode of the all-vanadium redox flow battery, which is 1.00 V; R is the gas constant, which is 8.314 J / (mol·K); is the temperature of the all-vanadium liquid flow battery at the i-th sampling, in K; F is the Faraday constant, which is 96485C / mol; is the concentration of hydrogen ions in the cathode electrolyte at the time of the i-th sampling, in mol / L; is the activity coefficient of hydrogen ions, which is taken as 1; is the standard concentration, 1 mol / L; is the power state of the all-vanadium liquid flow battery at the i-th sampling; is the activity coefficient of pentavalent vanadium ions in the positive electrode electrolyte, which is taken as 1; is the activity coefficient of tetravalent vanadium ions in the positive electrode electrolyte, which is taken as 1.

[0020] Furthermore, the equilibrium potential calculation formula of the negative electrode hydrogen evolution reaction is:

[0021] in, is the equilibrium potential of the negative electrode hydrogen evolution reaction at the i-th sampling, in V; is the exchange current density of the negative electrode vanadium ion reaction, taking 1E-4A / ; is the exchange current density of the negative electrode hydrogen evolution reaction, which is 1E-6 A / ; is the equilibrium potential of the vanadium ion reaction at the negative electrode during the i-th sampling, in V; is the negative electrode equilibrium mixed potential of the all-vanadium liquid flow battery at the i-th sampling time, in V.

[0022] The calculation formula for the equilibrium potential of the negative electrode vanadium ion reaction is:

[0023] in, is the standard equilibrium potential of the negative electrode vanadium ion reaction, which is -0.255V; is the activity coefficient of the divalent vanadium ion in the negative electrode electrolyte, which is taken as 1; is the activity coefficient of the trivalent vanadium ion in the negative electrode electrolyte, which is taken as 1; R is the gas constant, which is 8.314 J / (mol·K); is the temperature of the all-vanadium liquid flow battery at the i-th sampling, in K; F is the Faraday constant, which is 96485C / mol; is the power state of the all-vanadium liquid flow battery at the i-th sampling time.

[0024] Furthermore, the calculation formula for calculating the hydrogen ion concentration in the negative electrode electrolyte according to the equilibrium potential of the negative electrode hydrogen evolution reaction is:

[0025] in, is the equilibrium potential of the negative electrode hydrogen evolution reaction at the i-th sampling, in V; R is the gas constant, which is 8.314 J / (mol·K); is the temperature of the all-vanadium liquid flow battery at the i-th sampling, in K; F is the Faraday constant, which is 96485C / mol; is the activity coefficient of hydrogen ions, which is taken as 1; is the standard concentration, 1 mol / L; is the concentration of hydrogen ions in the negative electrode electrolyte at the i-th sampling, in mol / L; is the standard equilibrium potential of the hydrogen evolution reaction, which is 0 V.

[0026] Further, the amount of hydrogen ion substance used for hydrogen evolution is calculated according to the hydrogen ion concentration in the negative electrode electrolyte and the parallel equations, including: the amount of hydrogen ion substance consumed by the negative electrode due to the hydrogen evolution side reaction, the amount of hydrogen ion substance in the negative electrode electrolyte, the amount of hydrogen ion substance increment calculation formula caused by the migration of the negative electrode due to the electrochemical reaction, and the amount of hydrogen ion substance consumed by the negative electrode due to the electrochemical reaction. The calculation formula for the amount of hydrogen ion substance increased due to dissociation equilibrium, the negative electrode electrolyte The dissociation equilibrium equation and the negative electrode electrolyte The dissociation rate calculation formula is combined to solve the amount of hydrogen ion substance used for hydrogen evolution; The calculation formula for the amount of hydrogen ion substances consumed by the negative electrode due to the hydrogen evolution side reaction is:

[0027] in, is the amount of hydrogen ions consumed by the hydrogen evolution side reaction during the i-th sampling period, in mol; is the amount of hydrogen ions in the negative electrode electrolyte at the i-1th sampling, in mol; is the amount of hydrogen ion substance increase caused by the migration of the battery electrochemical reaction during the i-th sampling period, mol; is the number of samples in the ith sampling period due to The amount of hydrogen ion substance increased due to dissociation equilibrium, mol; is the amount of hydrogen ions in the negative electrode electrolyte at the time of the i-th sampling, mol; The calculation formula for the amount of hydrogen ion substance in the negative electrode electrolyte is:

[0028] in, is the concentration of hydrogen ions in the negative electrode electrolyte at the i-th sampling, in mol / L; is the volume of negative electrode electrolyte at the i-th sampling, in L; The calculation formula for the amount of hydrogen ion substance increment caused by the migration of the negative electrode due to the electrochemical reaction is:

[0029] in, is the power state of the all-vanadium liquid flow battery at the i-th sampling; is the power state of the all-vanadium liquid flow battery at the i-1th sampling time; is the total vanadium content of the positive electrolyte, in mol; The negative electrode The formula for calculating the amount of hydrogen ion substance increased due to dissociation equilibrium is:

[0030] in, is the electrolyte in the negative electrode at the time of sampling i The dissociation rate is in mol / (L*s); is the time interval of the i-th sampling period, in seconds; The negative electrode electrolyte The dissociation equilibrium equation is:

[0031] in, is the electrolyte in the negative electrode at the time of sampling i The amount of substance in mol; is the negative electrode electrolyte in the i-1th sampling The amount of substance in mol; The negative electrode electrolyte The dissociation rate calculation formula is:

[0032] in, is the rate parameter, which is 10 mol / (L*s); β is The degree of dissociation can be taken as 0.25; is the activity coefficient of hydrogen ions, which is taken as 1; for The activity coefficient is taken as 1.

[0033] Furthermore, the amount of the substance that precipitates hydrogen is calculated as follows:

[0034] in, is the total amount of hydrogen released from the initial moment to the i-th sampling, in mol; is the amount of hydrogen ions consumed by the hydrogen evolution side reaction during the i-th sampling period, in mol.

[0035] A real-time monitoring system for hydrogen evolution reaction in a liquid flow battery is applied to the real-time monitoring method for hydrogen evolution reaction in a liquid flow battery, and the system comprises: A data acquisition module is used to acquire real-time data in the battery management system; A positive electrode hydrogen ion concentration calculation module is used to calculate the hydrogen ion concentration in the positive electrode electrolyte in the flow battery using simultaneous equations; The negative electrode equilibrium mixed potential calculation module is used to calculate the negative electrode equilibrium mixed potential based on the hydrogen ion concentration in the positive electrode electrolyte and the positive electrode equilibrium potential; A negative electrode equilibrium potential calculation module is used to calculate the equilibrium potential of the negative electrode hydrogen evolution reaction based on the negative electrode equilibrium mixed potential; A negative electrode hydrogen ion concentration calculation module is used to calculate the hydrogen ion concentration in the negative electrode electrolyte according to the equilibrium potential of the negative electrode hydrogen evolution reaction; A hydrogen ion substance amount calculation module is used to calculate the amount of hydrogen ion substance used for hydrogen evolution according to the hydrogen ion concentration in the negative electrode electrolyte and the simultaneous equation; The hydrogen substance amount calculation module is used to calculate the amount of the substance that releases hydrogen according to the amount of the substance of the hydrogen ions used for hydrogen evolution.

[0036] The beneficial effects of the present invention are as follows: a real-time monitoring method for hydrogen evolution reaction of a liquid flow battery of the present invention comprises: acquiring real-time data in a battery management system; calculating the concentration of hydrogen ions in a positive electrode electrolyte in a liquid flow battery by using simultaneous equations; calculating the equilibrium mixed potential of the negative electrode according to the concentration of hydrogen ions in the positive electrode electrolyte and in combination with the equilibrium potential of the positive electrode; calculating the equilibrium potential of the negative electrode hydrogen evolution reaction according to the equilibrium mixed potential of the negative electrode; calculating the concentration of hydrogen ions in the negative electrode electrolyte according to the equilibrium potential of the negative electrode hydrogen evolution reaction; calculating the amount of hydrogen ion substance used for hydrogen evolution according to the concentration of hydrogen ions in the negative electrode electrolyte and the simultaneous equations; and calculating the amount of hydrogen gas precipitated substance according to the amount of hydrogen ion substance used for hydrogen evolution. The method for real-time monitoring of hydrogen evolution reaction in a liquid flow battery of the present invention uses real-time data of a battery management system BMS to establish an electrochemical calculation formula, and can dynamically monitor the hydrogen evolution side reaction of the liquid flow battery without the need to add a hydrogen concentration sensor, thereby eliminating the installation and maintenance costs of a hydrogen detection device and thus reducing costs; based on the real-time data of the BMS, the changing trend of the hydrogen evolution side reaction can be quickly reflected, thereby improving the real-time performance of the system; the hydrogen evolution current and the main reaction current are separated by a calculation model, and the additional consumption ratio of electrons by the side reaction, i.e., the hydrogen evolution current ratio, is directly quantified, and the result is not affected by fluctuations in operating conditions such as working current density, thereby improving the reliability of system data; and the method can be extended to other liquid flow batteries by only adjusting the ion expression, thereby having universality and strong compatibility. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] The present invention will be further described below in conjunction with the accompanying drawings and embodiments.

[0038] In the figure: Figure 1 A flow chart of a method for real-time monitoring of hydrogen evolution reaction in a liquid flow battery provided by the first embodiment of the present invention; Figure 2 A schematic diagram of a module of a real-time monitoring system for hydrogen evolution reaction in a flow battery provided by a second embodiment of the present invention; Figure 3 It is a structural diagram of a network-side server provided according to a third embodiment of the present invention. DETAILED DESCRIPTION

[0039] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0040] First embodiment: The first embodiment of the present invention provides a real-time monitoring method for hydrogen evolution reaction in a liquid flow battery, comprising: acquiring real-time data in a battery management system; calculating the concentration of hydrogen ions in a positive electrode electrolyte in the liquid flow battery by using simultaneous equations; calculating the equilibrium mixed potential of the negative electrode according to the concentration of hydrogen ions in the positive electrode electrolyte in combination with the equilibrium potential of the positive electrode; calculating the equilibrium potential of the negative electrode hydrogen evolution reaction according to the equilibrium mixed potential of the negative electrode; calculating the concentration of hydrogen ions in the negative electrode electrolyte according to the equilibrium potential of the negative electrode hydrogen evolution reaction; calculating the amount of hydrogen ions used for hydrogen evolution according to the concentration of hydrogen ions in the negative electrode electrolyte and the simultaneous equations; and calculating the amount of hydrogen gas released according to the amount of hydrogen ions used for hydrogen evolution. The method for real-time monitoring of hydrogen evolution reaction in a liquid flow battery of the present invention uses real-time data of a battery management system BMS to establish an electrochemical calculation formula, and can dynamically monitor the hydrogen evolution side reaction of the liquid flow battery without the need to add a hydrogen concentration sensor, thereby eliminating the installation and maintenance costs of a hydrogen detection device and thus reducing costs; based on the real-time data of the BMS, the changing trend of the hydrogen evolution side reaction can be quickly reflected, thereby improving the real-time performance of the system; the hydrogen evolution current and the main reaction current are separated by a calculation model, and the additional consumption ratio of electrons by the side reaction, i.e., the hydrogen evolution current ratio, is directly quantified, and the result is not affected by fluctuations in operating conditions such as working current density, thereby improving the reliability of system data; and the method can be extended to other liquid flow batteries by only adjusting the ion expression, thereby having universality and strong compatibility.

[0041] The following is a detailed description of the implementation details of the real-time monitoring method for hydrogen evolution reaction in a liquid flow battery of this embodiment. The following content is only provided for the convenience of understanding the implementation details and is not necessary for the implementation of this solution. The specific process of this embodiment is as follows: Figure 1 shown.

[0042] Step S1, obtaining real-time data in the battery management system.

[0043] Specifically, obtaining real-time data in the battery management system BMS includes: obtaining the state of charge SOC, open circuit voltage OCV, sampling time, sampling times, obtaining the total vanadium content in the positive electrode electrolyte, monitoring the volume of the positive and negative electrode electrolytes respectively, and collecting and calculating the average temperature of the electrolyte in the positive and negative electrode storage tanks of the liquid flow battery.

[0044] Furthermore, the volume of positive and negative electrolytes in the flow battery can be obtained through the liquid level monitoring data in the positive electrode storage tank and the negative electrode storage tank.

[0045] Furthermore, the average current of the flow battery can also be collected.

[0046] Step S2, using simultaneous equations to calculate the hydrogen ion concentration in the positive electrode electrolyte in the liquid flow battery.

[0047] Specifically, the simultaneous equations used to calculate the hydrogen ion concentration in the positive electrode electrolyte of the flow battery include: a calculation formula for the positive electrode hydrogen ion concentration, a conservation equation for the amount of hydrogen ions in the positive electrode, a calculation formula for the amount of hydrogen ion substances caused by the electrochemical reaction and migration of the positive electrode, and a calculation formula for the amount of hydrogen ion substances caused by the electrochemical reaction and migration of the positive electrode. The calculation formula for the amount of hydrogen ion substance increased due to dissociation equilibrium, the positive electrode electrolyte The dissociation equilibrium equation and the positive electrolyte The dissociation rate calculation formula is combined to solve the hydrogen ion concentration in the positive electrode electrolyte.

[0048] The calculation formula for the positive electrode hydrogen ion concentration is:

[0049] in, is the concentration of hydrogen ions in the cathode electrolyte at the time of the i-th sampling, in mol / L; is the amount of hydrogen ions in the positive electrode electrolyte at the time of the i-th sampling, in mol; is the volume of the positive electrode electrolyte at the time of the i-th sampling, in L, , is the total number of sampling times.

[0050] The substance conservation equation of the positive electrode hydrogen ion is:

[0051] in, is the amount of hydrogen ions in the positive electrode electrolyte at the i-1th sampling, in mol; is the amount of hydrogen ions in the positive electrode electrolyte caused by the battery electrochemical reaction and migration during the i-th sampling period, in mol; is the positive electrode electrolyte in the i-th sampling period due to The amount of hydrogen ion substance increased due to dissociation equilibrium, in mol.

[0052] Furthermore, the i-th sampling period is the period between the i-1-th sampling and the i-th sampling, and the first sampling period refers to the period between the initial moment and the first sampling moment; when i is 1, is the amount of hydrogen ions in the positive electrolyte at the initial moment, according to the initial concentration of sulfuric acid in the positive electrolyte and The dissociation equilibrium is obtained.

[0053] The calculation formula for the amount of hydrogen ion substance increment caused by the electrochemical reaction and migration of the positive electrode is:

[0054] in, is the power state of the all-vanadium liquid flow battery at the i-th sampling; is the power state of the all-vanadium liquid flow battery at the i-1th sampling time; is the total vanadium content of the positive electrode electrolyte, in mol.

[0055] Furthermore, the total vanadium content of the positive electrolyte The data read from the battery management system BMS can also be directly replaced by the initial total vanadium content of the positive electrode electrolyte.

[0056] The positive electrode The formula for calculating the amount of hydrogen ion substance increased due to dissociation equilibrium is:

[0057] in, is the electrolyte in the positive electrode at the time of sampling i The dissociation rate is in mol / (L*s); is the time interval of the ith sampling period, in seconds.

[0058] The positive electrode electrolyte The dissociation equilibrium equation is:

[0059] in, is the electrolyte in the positive electrode at the time of sampling i The amount of substance in mol; is the electrolyte in the positive electrode at the i-1th sampling The amount of substance in mol.

[0060] The positive electrode electrolyte The dissociation rate calculation formula is:

[0061] in, is the rate parameter, which can be 10 mol / (L*s); β is The degree of dissociation can be taken as 0.25; is the activity coefficient of hydrogen ions, which can be taken as 1; for The activity coefficient can be taken as 1.

[0062] When i is 1, Indicates the initial moment of positive electrolyte The amount of ion substance is determined by the initial concentration of sulfuric acid in the positive electrolyte and The dissociation equilibrium is obtained; Step S3, calculating the negative electrode equilibrium mixed potential according to the hydrogen ion concentration in the positive electrode electrolyte and the positive electrode equilibrium potential.

[0063] Specifically, the negative electrode equilibrium mixed potential calculation formula is:

[0064] in, is the negative electrode equilibrium mixed potential of the all-vanadium liquid flow battery at the i-th sampling time, in V; is the open circuit voltage of the all-vanadium liquid flow battery at the i-th sampling time, in V; is the positive electrode equilibrium potential of the all-vanadium liquid flow battery at the i-th sampling, in V.

[0065] Furthermore, the open circuit voltage of the vanadium liquid flow battery at the i-th sampling time is Obtained from the battery management system BMS.

[0066] The calculation formula for the positive electrode equilibrium potential of all-vanadium liquid flow battery is:

[0067] in, is the standard equilibrium potential of the positive electrode of the all-vanadium redox flow battery, which is 1.00 V; R is the gas constant, which is 8.314 J / (mol·K); is the temperature of the all-vanadium liquid flow battery at the i-th sampling, in K; F is the Faraday constant, which is 96485C / mol; is the activity coefficient of hydrogen ions, which can be taken as 1; is the standard concentration, 1 mol / L; is the power state of the all-vanadium liquid flow battery at the i-th sampling; is the activity coefficient of pentavalent vanadium ions in the positive electrode electrolyte, which can be taken as 1; is the activity coefficient of the tetravalent vanadium ion in the positive electrode electrolyte, which can be taken as 1.

[0068] Furthermore, the power state of the all-vanadium liquid flow battery at the i-th sampling time is Obtained from the battery management system BMS system; the temperature of the all-vanadium liquid flow battery at the i-th sampling , take the average temperature of the electrolyte in the positive and negative electrode storage tanks and obtain it from the battery management system BMS system.

[0069] Step S4, calculating the equilibrium potential of the negative electrode hydrogen evolution reaction according to the negative electrode equilibrium mixed potential.

[0070] Specifically, the equilibrium potential calculation formula of the negative electrode hydrogen evolution reaction is:

[0071] in, is the equilibrium potential of the negative electrode hydrogen evolution reaction at the i-th sampling, in V; is the exchange current density of the negative electrode vanadium ion reaction, which can be taken as 1E-4A / , can also be obtained through experiments; is the exchange current density of the negative electrode hydrogen evolution reaction, which can be taken as 1E-6 A / , can also be obtained through experiments; is the equilibrium potential of the vanadium ion reaction at the negative electrode during the i-th sampling, in V.

[0072] The calculation formula for the equilibrium potential of the negative electrode vanadium ion reaction is:

[0073] in, is the standard equilibrium potential of the negative electrode vanadium ion reaction, which is -0.255V; is the activity coefficient of the divalent vanadium ion in the negative electrode electrolyte, which can be taken as 1; is the activity coefficient of the trivalent vanadium ion in the negative electrode electrolyte, which can be taken as 1.

[0074] Step S5, calculating the hydrogen ion concentration in the negative electrode electrolyte according to the equilibrium potential of the negative electrode hydrogen evolution reaction.

[0075] Specifically, the calculation formula for calculating the hydrogen ion concentration in the negative electrode electrolyte according to the equilibrium potential of the negative electrode hydrogen evolution reaction is:

[0076] in, is the concentration of hydrogen ions in the negative electrode electrolyte at the i-th sampling, in mol / L; is the standard equilibrium potential of the hydrogen evolution reaction, which is 0 V.

[0077] Step S6, calculating the amount of the substance of hydrogen ions used for hydrogen evolution according to the hydrogen ion concentration in the negative electrode electrolyte and the simultaneous equations.

[0078] Specifically, the amount of hydrogen ion substance used for hydrogen evolution is calculated according to the hydrogen ion concentration in the negative electrode electrolyte and the parallel equations, including: the amount of hydrogen ion substance consumed by the negative electrode due to the hydrogen evolution side reaction, the amount of hydrogen ion substance in the negative electrode electrolyte, the amount of hydrogen ion substance increment calculation formula caused by the migration of the negative electrode due to the electrochemical reaction, and the amount of hydrogen ion substance consumed by the negative electrode due to the electrochemical reaction. The calculation formula for the amount of hydrogen ion substance increased due to dissociation equilibrium, the negative electrode electrolyte The dissociation equilibrium equation and the negative electrode electrolyte The dissociation rate calculation formula is combined to solve the amount of hydrogen ion substance used for hydrogen evolution.

[0079] The calculation formula for the amount of hydrogen ion substances consumed by the negative electrode due to the hydrogen evolution side reaction is:

[0080] in, is the amount of hydrogen ions consumed by the hydrogen evolution side reaction during the i-th sampling period, in mol; is the amount of hydrogen ions in the negative electrode electrolyte at the i-1th sampling, in mol; is the amount of hydrogen ion substance increase caused by the migration of the battery electrochemical reaction during the i-th sampling period, mol; is the number of samples in the ith sampling period due to The amount of hydrogen ion substance increased due to dissociation equilibrium, mol; is the amount of hydrogen ions in the negative electrode electrolyte at the i-th sampling, mol.

[0081] Furthermore, when i is 1, is the amount of hydrogen ions in the negative electrode electrolyte at the initial moment, according to the initial concentration of sulfuric acid in the negative electrode electrolyte and The dissociation equilibrium is obtained.

[0082] The calculation formula for the amount of hydrogen ion substance in the negative electrode electrolyte is:

[0083] in, is the concentration of hydrogen ions in the negative electrode electrolyte at the i-th sampling, in mol / L; is the volume of negative electrode electrolyte at the i-th sampling, in L.

[0084] The calculation formula for the amount of hydrogen ion substance increment caused by the migration of the negative electrode due to the electrochemical reaction is:

[0085] in, is the power state of the all-vanadium liquid flow battery at the i-th sampling; is the power state of the all-vanadium liquid flow battery at the i-1th sampling time; is the total vanadium content of the positive electrode electrolyte, in mol.

[0086] Furthermore, the total vanadium content of the positive electrolyte It can be read from the battery management system BMS or directly replaced by the initial total vanadium content of the positive electrode electrolyte.

[0087] The negative electrode The formula for calculating the amount of hydrogen ion substance increased due to dissociation equilibrium is:

[0088] in, is the electrolyte in the negative electrode at the time of sampling i The dissociation rate is in mol / (L*s); is the time interval of the ith sampling period, in seconds.

[0089] The negative electrode electrolyte The dissociation equilibrium equation is:

[0090] in, is the electrolyte in the negative electrode at the time of sampling i The amount of substance in mol; is the negative electrode electrolyte in the i-1th sampling The amount of substance in mol.

[0091] Furthermore, when i is 1, is the electrolyte in the negative electrode at the initial moment The amount of substance is determined by the initial concentration of sulfuric acid in the negative electrolyte and The dissociation equilibrium is obtained.

[0092] The negative electrode electrolyte The dissociation rate calculation formula is:

[0093] in, is the rate parameter, which can be 10 mol / (L*s); β is The degree of dissociation can be taken as 0.25; is the activity coefficient of hydrogen ions, which can be taken as 1; for The activity coefficient can be taken as 1.

[0094] Step S7, calculating the amount of the substance that releases hydrogen gas according to the amount of the substance of the hydrogen ions used for hydrogen release.

[0095] Specifically, the amount of the substance that precipitates hydrogen is calculated as follows:

[0096] in, It is the total amount of hydrogen released from the initial moment to the i-th sampling, in mol.

[0097] Step S8, calculating the hydrogen evolution rate and the hydrogen evolution current ratio according to the amount of the substance of the hydrogen ions used for hydrogen evolution.

[0098] Specifically, the hydrogen evolution rate calculation formula is:

[0099] in, is the hydrogen evolution rate in the ith sampling period, mol / s; The calculation formula for the hydrogen evolution current ratio is:

[0100] in, is the proportion of hydrogen evolution current in the i-th sampling period; is the average current in the i-th sampling period, in A.

[0101] The invention discloses a real-time monitoring method for hydrogen evolution reaction of a liquid flow battery, comprising: acquiring real-time data in a battery management system; calculating the concentration of hydrogen ions in a positive electrode electrolyte in the liquid flow battery by using simultaneous equations; calculating the equilibrium mixed potential of the negative electrode according to the concentration of hydrogen ions in the positive electrode electrolyte and in combination with the equilibrium potential of the positive electrode; calculating the equilibrium potential of the hydrogen evolution reaction at the negative electrode according to the equilibrium mixed potential of the negative electrode; calculating the concentration of hydrogen ions in the negative electrode electrolyte according to the equilibrium potential of the hydrogen evolution reaction at the negative electrode; calculating the amount of hydrogen ion substance used for hydrogen evolution according to the concentration of hydrogen ions in the negative electrode electrolyte and the simultaneous equations; and calculating the amount of hydrogen gas precipitating substance according to the amount of hydrogen ion substance used for hydrogen evolution. The method for real-time monitoring of hydrogen evolution reaction in a liquid flow battery of the present invention establishes an electrochemical calculation model using real-time data of a battery management system (BMS). The method can dynamically monitor the hydrogen evolution side reaction in the liquid flow battery without the need to install a hydrogen concentration sensor, thereby eliminating the installation and maintenance costs of a hydrogen detection device and reducing costs. Based on the real-time data of the BMS, the changing trend of the hydrogen evolution side reaction can be quickly reflected, thereby improving the real-time performance of the system. The method separates the hydrogen evolution current from the main reaction current through a calculation model, thereby directly quantifying the additional consumption ratio of electrons by the side reaction, namely, the hydrogen evolution current ratio. The result is not affected by fluctuations in operating conditions such as working current density, thereby improving the reliability of system data. The method can be extended to other liquid flow batteries by only adjusting the ion expression, thereby having universality and strong compatibility.

[0102] Second implementation method: like Figure 2 As shown, the second embodiment of the present invention provides a real-time monitoring system for hydrogen evolution reaction in a liquid flow battery, the system comprising: a data acquisition module 201, a positive electrode hydrogen ion concentration calculation module 202, a negative electrode equilibrium mixed potential calculation module 203, a negative electrode equilibrium potential calculation module 204, a negative electrode hydrogen ion concentration calculation module 205, a hydrogen ion substance amount calculation module 206, and a hydrogen gas substance amount calculation module 207.

[0103] Specifically, the data acquisition module 201 is used to acquire real-time data in the battery management system; the positive electrode hydrogen ion concentration calculation module 202 is used to calculate the hydrogen ion concentration in the positive electrode electrolyte in the liquid flow battery by using simultaneous equations; the negative electrode equilibrium mixed potential calculation module 203 is used to calculate the negative electrode equilibrium mixed potential according to the hydrogen ion concentration in the positive electrode electrolyte in combination with the positive electrode equilibrium potential; the negative electrode equilibrium potential calculation module 204 is used to calculate the equilibrium potential of the negative electrode hydrogen evolution reaction according to the negative electrode equilibrium mixed potential; the negative electrode hydrogen ion concentration calculation module 205 is used to calculate the hydrogen ion concentration in the negative electrode electrolyte according to the equilibrium potential of the negative electrode hydrogen evolution reaction; the hydrogen ion substance amount calculation module 206 is used to calculate the substance amount of hydrogen ions used for hydrogen evolution according to the hydrogen ion concentration in the negative electrode electrolyte and the simultaneous equations; the hydrogen gas substance amount calculation module 207 is used to calculate the amount of hydrogen gas precipitated according to the substance amount of hydrogen ions used for hydrogen evolution.

[0104] It is not difficult to find that this embodiment is a system embodiment corresponding to the first embodiment, and this embodiment can be implemented in conjunction with the first embodiment. The relevant technical details mentioned in the first embodiment are still valid in this embodiment, and in order to reduce repetition, they are not repeated here. Accordingly, the relevant technical details mentioned in this embodiment can also be applied in the first embodiment.

[0105] It is worth mentioning that all modules involved in this embodiment are logic modules. In practical applications, a logic unit can be a physical unit, a part of a physical unit, or a combination of multiple physical units. In addition, in order to highlight the innovative part of the present invention, this embodiment does not introduce units that are not closely related to solving the technical problem proposed by the present invention, but this does not mean that there are no other units in this embodiment.

[0106] A third embodiment of the present invention relates to a network side server, such as Figure 3 As shown, it includes at least one processor 302; and a memory 301 that is communicatively connected to the at least one processor 302; wherein the memory 301 stores instructions that can be executed by the at least one processor 302, and the instructions are executed by the at least one processor 302 so that the at least one processor 302 can execute the above-mentioned data processing method.

[0107] The memory 301 and the processor 302 are connected in a bus manner, and the bus may include any number of interconnected buses and bridges, and the bus connects various circuits of one or more processors 302 and the memory 301 together. The bus can also connect various other circuits such as peripheral devices, voltage regulators, and power management circuits, which are well known in the art and are therefore not further described herein. The bus interface provides an interface between the bus and the transceiver. The transceiver can be one element or multiple elements, such as multiple receivers and transmitters, providing a unit for communicating with various other devices on a transmission medium. The data processed by the processor 302 is transmitted on a wireless medium via an antenna, and further, the antenna also receives data and transmits the data to the processor 302.

[0108] The processor 302 is responsible for managing the bus and general processing, and can also provide various functions, including timing, peripheral interfaces, voltage regulation, power management and other control functions. The memory 301 can be used to store data used by the processor 302 when performing operations.

[0109] The fourth embodiment of the present invention relates to a computer-readable storage medium storing a computer program, which, when executed by a processor, implements the method for real-time monitoring of hydrogen evolution reaction in a liquid flow battery in the first embodiment.

[0110] That is, those skilled in the art can understand that all or part of the steps in the above-mentioned embodiment method can be completed by instructing the relevant hardware through a program, and the program is stored in a storage medium, including several instructions to enable a device (which can be a single-chip microcomputer, chip, etc.) or a processor to execute all or part of the steps of the method described in each embodiment of the present application. The aforementioned storage medium includes: U disk, mobile hard disk, read-only memory (ROM, Read-Only Memory), random access memory (RAM, Random Access Memory), disk or optical disk and other media that can store program codes.

[0111] The above is only an embodiment of the present invention. The common sense such as the known specific structure and characteristics in the scheme is not described in detail here. The ordinary technicians in the relevant field know all the common technical knowledge in the technical field of the invention before the application date or priority date, can obtain all the existing technologies in the field, and have the ability to apply the conventional experimental means before that date. The ordinary technicians in the relevant field can improve and implement this scheme in combination with their own abilities under the enlightenment given by this application. Some typical known structures or known methods should not become obstacles for ordinary technicians in the relevant field to implement this application. It should be pointed out that for those skilled in the art, without departing from the structure of the present invention, several deformations and improvements can be made, which should also be regarded as the protection scope of the present invention, which will not affect the effect of the implementation of the present invention and the practicality of the patent. The protection scope required by this application shall be based on the content of its claims, and the specific implementation methods and other records in the specification can be used to interpret the content of the claims.

[0112] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A real-time monitoring method for hydrogen evolution reaction in a liquid flow battery, characterized in that: include: Obtain real-time data within the battery management system; The simultaneous equations are used to calculate the hydrogen ion concentration in the positive electrolyte of the flow battery; According to the concentration of hydrogen ions in the positive electrode electrolyte, the negative electrode equilibrium mixed potential is calculated in combination with the positive electrode equilibrium potential; Calculate the equilibrium potential of the negative electrode hydrogen evolution reaction based on the negative electrode equilibrium mixed potential; Calculate the hydrogen ion concentration in the negative electrode electrolyte according to the equilibrium potential of the negative electrode hydrogen evolution reaction; Calculate the amount of hydrogen ion substance used for hydrogen evolution based on the hydrogen ion concentration in the negative electrode electrolyte and the simultaneous equation; The amount of the substance that releases hydrogen is calculated based on the amount of the substance that produces hydrogen ions.

2. The method for real-time monitoring of hydrogen evolution reaction in a flow battery according to claim 1, characterized in that: The real-time data acquisition in the battery management system includes: acquiring the state of charge SOC, open circuit voltage OCV, sampling time, sampling times, acquiring the total vanadium content in the positive electrode electrolyte, monitoring the volume of the positive and negative electrode electrolytes respectively, and collecting and calculating the average temperature of the electrolyte in the positive electrode storage tank and the negative electrode storage tank of the liquid flow battery.

3. The method for real-time monitoring of hydrogen evolution reaction in a liquid flow battery according to claim 1, characterized in that: The method of using simultaneous equations to calculate the concentration of hydrogen ions in the positive electrode electrolyte of the flow battery includes: calculating the positive electrode hydrogen ion concentration calculation formula, the positive electrode hydrogen ion substance conservation equation, the positive electrode hydrogen ion substance amount increment calculation formula due to electrochemical reaction and migration, and the positive electrode due to The calculation formula for the amount of hydrogen ion substance increased due to dissociation equilibrium, the positive electrode electrolyte The dissociation equilibrium equation and the positive electrolyte The dissociation rate calculation formula is combined to solve the hydrogen ion concentration in the positive electrode electrolyte.

4. The method for real-time monitoring of hydrogen evolution reaction in a liquid flow battery according to claim 3, characterized in that: The calculation formula for the positive electrode hydrogen ion concentration is: in, is the concentration of hydrogen ions in the cathode electrolyte at the time of the i-th sampling, in mol / L; is the amount of hydrogen ions in the positive electrode electrolyte at the time of the i-th sampling, in mol; is the volume of the cathode electrolyte at the i-th sampling, in L; The substance conservation equation of the positive electrode hydrogen ion is: in, is the amount of hydrogen ions in the positive electrode electrolyte at the i-1th sampling, in mol; is the amount of hydrogen ions in the positive electrode electrolyte caused by the battery electrochemical reaction and migration during the i-th sampling period, in mol; is the positive electrode electrolyte in the i-th sampling period due to The amount of hydrogen ions increased due to dissociation equilibrium, in mol; The calculation formula for the amount of hydrogen ion substance increment caused by the electrochemical reaction and migration of the positive electrode is: in, is the power state of the all-vanadium liquid flow battery at the i-th sampling; is the power state of the all-vanadium liquid flow battery at the i-1th sampling time; is the total vanadium content of the positive electrolyte, in mol; The positive electrode The formula for calculating the amount of hydrogen ion substance increased due to dissociation equilibrium is: in, is the electrolyte in the positive electrode at the time of sampling i The dissociation rate is in mol / (L*s); is the time interval of the i-th sampling period, in seconds; The positive electrode electrolyte The dissociation equilibrium equation is: in, is the electrolyte in the positive electrode at the time of sampling i The amount of substance in mol; is the electrolyte in the positive electrode at the i-1th sampling The amount of substance in mol; The positive electrode electrolyte The dissociation rate calculation formula is: in, is the rate parameter, the unit is mol / (L*s); β is Degree of dissociation; is the activity coefficient of hydrogen ions; for The activity coefficient.

5. The method for real-time monitoring of hydrogen evolution reaction in a liquid flow battery according to claim 1, characterized in that: The negative electrode equilibrium mixed potential calculation formula is: in, is the negative electrode equilibrium mixed potential of the all-vanadium liquid flow battery at the i-th sampling time, in V; is the open circuit voltage of the all-vanadium liquid flow battery at the i-th sampling time, in V; is the positive electrode equilibrium potential of the all-vanadium liquid flow battery at the i-th sampling, in V; The calculation formula for the positive electrode equilibrium potential of all-vanadium liquid flow battery is: in, is the standard equilibrium potential of the positive electrode of the all-vanadium redox flow battery, which is 1.00 V; R is the gas constant, which is 8.314 J / (mol·K); is the temperature of the all-vanadium liquid flow battery at the i-th sampling, in K; F is the Faraday constant, which is 96485C / mol; is the concentration of hydrogen ions in the cathode electrolyte at the time of the i-th sampling, in mol / L; is the activity coefficient of hydrogen ions; is the standard concentration, 1 mol / L; is the power state of the all-vanadium liquid flow battery at the i-th sampling; is the activity coefficient of pentavalent vanadium ions in the positive electrode electrolyte; is the activity coefficient of tetravalent vanadium ions in the positive electrode electrolyte.

6. The method for real-time monitoring of hydrogen evolution reaction in a liquid flow battery according to claim 1, characterized in that: The equilibrium potential calculation formula of the negative electrode hydrogen evolution reaction is: in, is the equilibrium potential of the negative electrode hydrogen evolution reaction at the i-th sampling, in V; is the exchange current density of the negative electrode vanadium ion reaction, in A / ; is the exchange current density of the negative electrode hydrogen evolution reaction, in A / ; is the equilibrium potential of the vanadium ion reaction at the negative electrode during the i-th sampling, in V; is the negative electrode equilibrium mixed potential of the all-vanadium liquid flow battery at the i-th sampling time, in V; The calculation formula for the equilibrium potential of the negative electrode vanadium ion reaction is: in, is the standard equilibrium potential of the negative electrode vanadium ion reaction, which is -0.255V; is the activity coefficient of the divalent vanadium ion in the negative electrode electrolyte; is the activity coefficient of the trivalent vanadium ion in the negative electrode electrolyte; R is the gas constant, which is 8.314 J / (mol·K); is the temperature of the all-vanadium liquid flow battery at the i-th sampling, in K; F is the Faraday constant, which is 96485C / mol; is the power state of the all-vanadium liquid flow battery at the i-th sampling.

7. The method for real-time monitoring of hydrogen evolution reaction in a liquid flow battery according to claim 1, characterized in that: The calculation formula for calculating the hydrogen ion concentration in the negative electrode electrolyte according to the equilibrium potential of the negative electrode hydrogen evolution reaction is: in, is the equilibrium potential of the hydrogen evolution reaction at the negative electrode during the i-th sampling, in V; R is the gas constant, which is 8.314 J / (mol·K); is the temperature of the all-vanadium liquid flow battery at the i-th sampling, in K; F is the Faraday constant, which is 96485C / mol; is the activity coefficient of hydrogen ions; is the standard concentration, 1 mol / L; is the concentration of hydrogen ions in the negative electrode electrolyte at the i-th sampling, in mol / L; is the standard equilibrium potential of the hydrogen evolution reaction, which is 0 V.

8. The method for real-time monitoring of hydrogen evolution reaction in a liquid flow battery according to claim 1, characterized in that: The method for calculating the amount of hydrogen ion substance used for hydrogen evolution according to the hydrogen ion concentration in the negative electrode electrolyte and the parallel equations includes: a calculation formula for the amount of hydrogen ion substance consumed by the negative electrode due to the hydrogen evolution side reaction, a calculation formula for the amount of hydrogen ion substance in the negative electrode electrolyte, a calculation formula for the amount of hydrogen ion substance increment caused by the migration of the negative electrode due to the electrochemical reaction, and a calculation formula for the amount of hydrogen ion substance consumed by the negative electrode due to the hydrogen evolution side reaction. The calculation formula for the amount of hydrogen ion substance increased due to dissociation equilibrium, the negative electrode electrolyte The dissociation equilibrium equation and the negative electrode electrolyte The dissociation rate calculation formula is combined to solve the amount of hydrogen ion substance used for hydrogen evolution.

9. The method for real-time monitoring of hydrogen evolution reaction in a flow battery according to claim 8, characterized in that: The calculation formula for the amount of hydrogen ion substances consumed by the negative electrode due to the hydrogen evolution side reaction is: in, is the amount of hydrogen ions consumed by the hydrogen evolution side reaction during the i-th sampling period, in mol; is the amount of hydrogen ions in the negative electrode electrolyte at the i-1th sampling, in mol; is the amount of hydrogen ion substance increase caused by the migration of the battery electrochemical reaction during the i-th sampling period, mol; is the number of samples in the ith sampling period due to The amount of hydrogen ion substance increased due to dissociation equilibrium, mol; is the amount of hydrogen ions in the negative electrode electrolyte at the time of the i-th sampling, mol; The calculation formula for the amount of hydrogen ion substance in the negative electrode electrolyte is: in, is the concentration of hydrogen ions in the negative electrode electrolyte at the i-th sampling, in mol / L; is the volume of negative electrode electrolyte at the i-th sampling, in L; The calculation formula for the amount of hydrogen ion substance increment caused by the migration of the negative electrode due to the electrochemical reaction is: in, is the power state of the all-vanadium liquid flow battery at the i-th sampling; is the power state of the all-vanadium liquid flow battery at the i-1th sampling time; is the total vanadium content of the positive electrolyte, in mol; The negative electrode The formula for calculating the amount of hydrogen ion substance increased due to dissociation equilibrium is: in, is the electrolyte in the negative electrode at the time of sampling i The dissociation rate is in mol / (L*s); is the time interval of the i-th sampling period, in seconds; The negative electrode electrolyte The dissociation equilibrium equation is: in, is the electrolyte in the negative electrode at the time of sampling i The amount of substance in mol; is the negative electrode electrolyte in the i-1th sampling The amount of substance in mol; The negative electrode electrolyte The dissociation rate calculation formula is: in, is the rate parameter, the unit is mol / (L*s); β is Degree of dissociation; is the activity coefficient of hydrogen ions; for The activity coefficient.

10. A real-time monitoring system for hydrogen evolution reaction in a liquid flow battery, characterized in that: The method for real-time monitoring of hydrogen evolution reaction in a liquid flow battery according to any one of claims 1 to 9, the system comprising: A data acquisition module is used to acquire real-time data in the battery management system; A positive electrode hydrogen ion concentration calculation module is used to calculate the hydrogen ion concentration in the positive electrode electrolyte in the flow battery using simultaneous equations; The negative electrode equilibrium mixed potential calculation module is used to calculate the negative electrode equilibrium mixed potential based on the hydrogen ion concentration in the positive electrode electrolyte and the positive electrode equilibrium potential; A negative electrode equilibrium potential calculation module is used to calculate the equilibrium potential of the negative electrode hydrogen evolution reaction based on the negative electrode equilibrium mixed potential; A negative electrode hydrogen ion concentration calculation module is used to calculate the hydrogen ion concentration in the negative electrode electrolyte according to the equilibrium potential of the negative electrode hydrogen evolution reaction; A hydrogen ion substance amount calculation module is used to calculate the amount of hydrogen ion substance used for hydrogen evolution according to the hydrogen ion concentration in the negative electrode electrolyte and the simultaneous equation; The hydrogen substance amount calculation module is used to calculate the amount of the substance that releases hydrogen according to the amount of the substance of the hydrogen ions used for hydrogen evolution.

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