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CN109669142B - Method and system for monitoring vanadium migration of all-vanadium redox flow battery in real time - Google Patents

Method and system for monitoring vanadium migration of all-vanadium redox flow battery in real time Download PDF

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CN109669142B
CN109669142B CN201811140235.5A CN201811140235A CN109669142B CN 109669142 B CN109669142 B CN 109669142B CN 201811140235 A CN201811140235 A CN 201811140235A CN 109669142 B CN109669142 B CN 109669142B
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于彩红
董艳影
赵叶龙
邹毅
刘宗浩
宋玉波
王良
梁加富
高新亮
王丹
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Abstract

本发明公开了一种用于实时监测全钒液流电池钒迁移的方法及系统，其包括：获取采样数据，即通过SOC检测装置对不同浓度的正负极电解液相对于参比溶液的电位参数进行采样，同时对正极电解液总体积、负极电解液总体积进行采集；通过采样数据拟合出正/负极电解液电位经验公式；建立电解液浓度监测数据库并确定待测正/负极电解液中各个价态钒离子浓度；基于所确定的待测正/负极电解液中各个价态钒离子浓度，计算出正/负极总钒量，进而得出系统钒迁移量；基于所计算的系统钒迁移量，向钒迁移的反方向调整电解液使正负极钒量恢复到初始最佳比例使得系统容量得到恢复。本发明能够便捷得到系统钒迁移量，从而达到抑制由钒迁移导致的容量衰减。

Figure 201811140235

The invention discloses a method and a system for real-time monitoring of vanadium migration in an all-vanadium redox flow battery. The parameters are sampled, and the total volume of the positive electrolyte and the total volume of the negative electrolyte are collected at the same time; the positive/negative electrolyte potential empirical formula is fitted through the sampling data; the electrolyte concentration monitoring database is established and the positive/negative electrolyte to be tested is determined. each valence vanadium ion concentration in The amount of migration, the electrolyte is adjusted in the opposite direction of vanadium migration, so that the amount of vanadium in the positive and negative electrodes is restored to the initial optimum ratio, so that the system capacity is restored. The present invention can conveniently obtain the system vanadium migration amount, thereby suppressing the capacity attenuation caused by vanadium migration.

Figure 201811140235

Description

Method and system for monitoring vanadium migration of all-vanadium redox flow battery in real time
Technical Field
The invention relates to a flow battery technology, in particular to a method and a system for monitoring vanadium migration of an all-vanadium flow battery in real time.
Background
With the progress of charging and discharging of the vanadium battery system, vanadium ions in the electrolyte can migrate through the membrane, thereby affecting the system capacity.
At present, the solutions in the prior art have the following problems:
1. the ionic membrane in the galvanic pile is replaced, and the membrane with better vanadium resistance effect is used, but the technology is not mature at present;
2. electrolyte is adjusted from one side with more vanadium to one side with less vanadium regularly, but the vanadium migration direction and the migration amount of the system are different along with the difference of the operation mode; and as the vanadium battery system is charged and discharged, vanadium ions in the electrolyte can migrate through the membrane, thereby affecting the system capacity.
In summary, the existing method for monitoring the concentration state of the electrolyte of the flow battery on line has certain disadvantages, particularly certain deviation change conditions, and cannot meet the use requirement for monitoring the state of the electrolyte of the flow battery in real time.
Disclosure of Invention
In view of the disadvantages in the prior art, the present invention provides a method for monitoring vanadium migration of an all-vanadium redox flow battery in real time, so as to effectively solve the technical problems mentioned in the background art.
A method for monitoring vanadium migration of an all-vanadium redox flow battery in real time is characterized by comprising the following steps:
s1, acquiring sampling data, namely sampling potential parameters of the positive and negative electrolytes with different concentrations relative to a reference solution through an SOC detection device, and simultaneously acquiring the total volume of the positive electrolyte and the total volume of the negative electrolyte; the SOC detection device comprises an end plate, a first bipolar plate, a positive/negative electrolyte detection cavity, an ion exchange membrane, a positive electrolyte inlet/outlet pipeline and a negative electrolyte inlet/outlet pipeline which are respectively communicated with the positive/negative electrolyte detection cavity, a plurality of insulation plates provided with first through holes, a reference detection cavity and a second bipolar plate which is arranged in the reference detection cavity and used as a potential test electrode, wherein the insulation plates are respectively arranged on two sides of the ion exchange membrane to separate the reference detection cavity from the positive/negative electrolyte detection cavity; a reference solution is filled in the reference detection cavity;
s2, fitting an empirical formula of the positive/negative electrolyte potential through the sampling data;
wherein the anode electrolyte potential empirical formula is
Figure BDA0001815634320000021
The potential empirical formula of the cathode electrolyte is
Figure BDA0001815634320000022
In the formula, EIs just、ENegative poleThe potential of the electrolyte of the positive electrode and the potential of the electrolyte of the negative electrode are respectively in mV;
Figure BDA0001815634320000023
Figure BDA0001815634320000024
the concentrations of the vanadium ions with valence of 2, 3, 4 and 5 are respectively; a. theIs justIs an empirical formula constant term of the positive electrode potential; b isIs justThe potential empirical formula of the positive electrode is the 4-valent vanadium ion coefficient; cIs justThe potential empirical formula of the positive electrode is the 5-valent vanadium ion coefficient; a. theNegative poleIs a constant term of an empirical formula of the cathode potential; b isNegative poleThe cathode potential empirical formula is the 2-valent vanadium ion coefficient; cNegative poleThe empirical formula of the potential of the negative electrode is the coefficient of the vanadium ions with the valence of 3;
s3, establishing an electrolyte concentration monitoring database and determining the concentration of each valence state vanadium ion in the positive/negative electrode electrolyte to be detected, wherein the electrolyte concentration monitoring database comprises at least one formula or inequality of a positive/negative electrode electrolyte potential empirical formula, a vanadium total mass conservation formula and a selectable formula/inequality, and the selectable formula/inequality comprises a system average valence state formula, a positive electrode vanadium total mass conservation formula, a negative electrode vanadium total mass conservation formula, a positive electrode vanadium concentration interval inequality and a negative electrode vanadium concentration interval inequality;
s4, calculating the total vanadium content of the positive/negative electrodes based on the determined concentration of each valence state vanadium ion in the positive/negative electrode electrolyte to be detected, and further obtaining the vanadium migration amount of the system;
s5, based on the calculated vanadium migration amount of the system, adjusting the electrolyte in the opposite direction of vanadium migration to restore the vanadium amount of the anode and the cathode to the initial optimal proportion so as to restore the system capacity;
wherein the vanadium migration amount calculation formula is as follows:
Figure BDA0001815634320000025
Figure BDA0001815634320000026
Figure BDA0001815634320000027
in the formula, NIs just、NNegative poleThe total amount of vanadium ions on the positive and negative sides respectively,
Figure BDA0001815634320000028
Figure BDA0001815634320000029
respectively the concentration of 2, 3, 4 and 5 valent vanadium ions, VIs just、VNegative poleRespectively the volume of the positive electrode electrolyte, the volume of the negative electrode electrolyte, NMigrationThe transfer amount of vanadium ions;
the adjustment strategy for adjusting the electrolyte in the direction opposite to the vanadium migration direction is as follows: if N is presentMigrationIf the electrolyte is positive, the electrolyte needs to be adjusted from the positive electrode to the negative electrode, and the adjustment volume is as follows:
Figure BDA0001815634320000031
if N is presentMigrationIf the electrolyte is a negative value, the electrolyte needs to be adjusted from the negative electrode to the positive electrode, and the adjustment volume is as follows:
Figure BDA0001815634320000032
wherein the vanadium total mass conservation formula is
Figure BDA0001815634320000033
In the formula VIs just、VNegative poleRespectively the volume of the electrolyte of the positive electrode and the negative electrode, NGeneral assemblyThe unit is the total amount of vanadium ions in each valence state in the battery system and is mol;
formula of average valence state of said system
Figure BDA0001815634320000034
Wherein M is the average valence of vanadium ions in each valence state of the system;
the positive electrode vanadium total conservation formula
Figure BDA0001815634320000035
In the formula, NIs justThe unit mol is the total amount of vanadium ions on the positive electrode side;
the cathode vanadium total conservation formula;
Figure BDA0001815634320000036
in the formula, NNegative poleThe unit mol is the total amount of vanadium ions on the negative electrode side;
the positive electrode vanadium concentration interval inequality
Figure BDA0001815634320000037
In the formula, cInitial assemblyThe concentration value of the electrolyte initially added into the system;
the negative electrode vanadium concentration interval inequality
Figure BDA0001815634320000041
In the formula, cInitial assemblyIs the concentration value of the electrolyte initially charged into the system.
Furthermore, when data sampling is carried out, in the variation range of the composition of the positive and negative electrolytes of the all-vanadium redox flow energy storage battery system, sampling is carried out under the condition that the variation interval of the vanadium ion concentration of different valence states is not more than 0.2mol/L, the total vanadium concentration sampling points of the positive and negative electrolytes are not less than 3, and the hydrogen ion concentration sampling points are not less than 3.
Furthermore, the detection cavity of the SOC detection device is composed of a reference detection cavity and at least one electrolyte detection cavity of a positive electrolyte detection cavity and a negative electrolyte detection cavity.
Furthermore, the reference detection cavity is provided with a second through hole for the circulation and the updating of the reference solution.
Further, the reference solution is an electrolyte with vanadium ions.
Further, the valence range of the vanadium ion in the electrolyte is 3.5 valence or one of mixed valence of 4 valence and 5 valence.
Furthermore, a cavity is formed in the part, placed in the reference detection cavity, of the second bipolar plate, and the proportion range of the opening area of the cavity to the total area of the electrodes in the reference detection cavity is 0-1.
Further, the second bipolar plate is made of any one of a carbon material, a metal material and a conductive polymer.
Furthermore, the aperture of the first through hole is filled with a material with high specific surface area or a hydrophilic material.
Furthermore, the first through hole is a straight hole or a bent hole extending and bending along the thickness direction of the insulating plate.
Further, the insulating plate is made of any one of a PP insulating material, a PE insulating material, a PVC insulating material, a PVDF insulating material and a PTFE insulating material.
The invention provides a system capable of monitoring the side reaction of the all-vanadium redox flow battery in real time, which is characterized by comprising the following components:
the data sampling unit is used for sampling potential parameters of the positive and negative electrolytes with different concentrations relative to a reference solution through the SOC detection device and simultaneously collecting the total volume of the positive electrolyte and the total volume of the negative electrolyte; the SOC detection device comprises an end plate, a first bipolar plate, a positive/negative electrolyte detection cavity, an ion exchange membrane, a positive electrolyte inlet/outlet pipeline and a negative electrolyte inlet/outlet pipeline which are respectively communicated with the positive/negative electrolyte detection cavity, a plurality of insulation plates provided with first through holes, a reference detection cavity and a second bipolar plate which is arranged in the reference detection cavity and used as a potential test electrode, wherein the insulation plates are respectively arranged on two sides of the ion exchange membrane to separate the reference detection cavity from the positive/negative electrolyte detection cavity; a reference solution is filled in the reference detection cavity;
the sampling data fitting unit is used for fitting an empirical formula of the potential of the positive/negative electrolyte through the sampling data acquired by the data sampling unit;
wherein the anode electrolyte potential empirical formula is
Figure BDA0001815634320000051
The potential empirical formula of the cathode electrolyte is
Figure BDA0001815634320000052
In the formula, EIs just、ENegative poleThe potentials of the positive electrolyte and the negative electrolyte are respectively in mV;
Figure BDA0001815634320000053
Figure BDA0001815634320000054
the concentrations of the vanadium ions with valence of 2, 3, 4 and 5 are respectively; a. theIs justDetermining an empirical formula constant term of positive potential of each valence vanadium ion concentration in the positive/negative electrolyte to be detected; b isIs justThe potential empirical formula of the positive electrode is the 4-valent vanadium ion coefficient; cIs justThe potential empirical formula of the positive electrode is the 5-valent vanadium ion coefficient; a. theNegative poleIs a constant term of an empirical formula of the cathode potential; b isNegative poleThe cathode potential empirical formula is the 2-valent vanadium ion coefficient; cNegative poleThe empirical formula of the potential of the negative electrode is the coefficient of the vanadium ions with the valence of 3;
the concentration monitoring unit is used for determining the concentration of each valence state vanadium ion in the positive/negative electrode electrolyte to be detected based on the established electrolyte concentration monitoring database, the electrolyte concentration monitoring database comprises at least one formula or inequality of a positive/negative electrode electrolyte potential empirical formula, a vanadium total mass conservation formula and a selectable formula/inequality, and the concentration of each valence state vanadium ion in the positive/negative electrode electrolyte to be detected is determined, wherein the selectable formula/inequality comprises a system average valence state formula, a positive electrode vanadium total mass conservation formula, a negative electrode vanadium total mass conservation formula, a positive electrode vanadium concentration interval inequality and a negative electrode vanadium concentration interval inequality;
the system vanadium migration amount calculation unit is used for calculating the total vanadium amount of the positive/negative electrodes based on the determined concentration of each valence vanadium ion in the positive/negative electrode electrolyte to be detected, so as to obtain the system vanadium migration amount;
and the capacity recovery unit is used for adjusting the electrolyte in the reverse direction of vanadium migration based on the calculated vanadium migration amount of the system so as to recover the vanadium amount of the anode and the cathode to the initial optimal proportion and recover the capacity of the system.
Wherein the vanadium migration amount calculation formula is as follows:
Figure BDA0001815634320000061
Figure BDA0001815634320000062
Figure BDA0001815634320000063
in the formula, NIs just、NNegative poleThe total amount of vanadium ions on the positive and negative sides respectively,
Figure BDA0001815634320000064
Figure BDA0001815634320000065
respectively the concentration of 2, 3, 4 and 5 valent vanadium ions, VIs just、VNegative poleRespectively the volume of the positive electrode electrolyte, the volume of the negative electrode electrolyte, NMigrationThe transfer amount of vanadium ions;
the adjustment strategy for adjusting the electrolyte in the direction opposite to the vanadium migration direction is as follows: if N is presentMigrationIf the electrolyte is positive, the electrolyte needs to be adjusted from the positive electrode to the negative electrode, and the adjustment volume is as follows:
Figure BDA0001815634320000066
if N is presentMigrationIf the electrolyte is a negative value, the electrolyte needs to be adjusted from the negative electrode to the positive electrode, and the adjustment volume is as follows:
Figure BDA0001815634320000067
wherein the vanadium total mass conservation formula is
Figure BDA0001815634320000068
In the formula VIs just、VNegative poleRespectively the volume of the electrolyte of the positive electrode and the negative electrode, NGeneral assemblyThe unit is the total amount of vanadium ions in each valence state in the battery system and is mol;
formula of average valence state of said system
Figure BDA0001815634320000069
Wherein M is the average valence of vanadium ions in each valence state of the system;
the positive electrode vanadium total conservation formula
Figure BDA00018156343200000610
In the formula, NIs justThe unit mol is the total amount of vanadium ions on the positive electrode side;
the cathode vanadium total conservation formula;
Figure BDA0001815634320000071
in the formula, NNegative poleThe unit mol is the total amount of vanadium ions on the negative electrode side;
the positive electrode vanadium concentration interval inequality
Figure BDA0001815634320000072
In the formula, cInitial assemblyThe concentration value of the electrolyte initially added into the system;
the negative electrode vanadium concentration interval inequality
Figure BDA0001815634320000073
In the formula, cInitial assemblyIs the concentration value of the electrolyte initially charged into the system.
Furthermore, when data sampling is carried out, in the variation range of the composition of the positive and negative electrolytes of the all-vanadium redox flow energy storage battery system, sampling is carried out under the condition that the variation interval of the vanadium ion concentration of different valence states is not more than 0.2mol/L, the total vanadium concentration sampling points of the positive and negative electrolytes are not less than 3, and the hydrogen ion concentration sampling points are not less than 3.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the vanadium migration volume of the system can be conveniently obtained by only acquiring the four parameters of the volume of the positive and negative electrolytes of the system and the potential difference of the positive and negative electrolytes relative to the reference solution, so that the capacity attenuation caused by vanadium migration is inhibited, namely when the vanadium migration reaches the degree of influencing the capacity of the system, the electrolyte is adjusted, the vanadium volume of the positive and negative electrodes is balanced again, and the capacity of the system is recovered.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic structural diagram of an SOC detection apparatus according to an embodiment of the present invention;
fig. 2 is a schematic diagram of a first second bipolar plate structure of an SOC detection device according to an embodiment of the present invention;
fig. 3 is a schematic diagram of a second bipolar plate structure of an SOC detection device according to an embodiment of the present invention;
FIG. 4 is a schematic structural diagram of an insulation board of an SOC detection apparatus according to an embodiment of the present invention;
FIG. 5 is a schematic diagram of a SOC detection apparatus-reference solution flow-through refresh architecture according to an embodiment of the present invention;
FIGS. 6-7 are diagrams of examples of system discharge capacities according to embodiments of the present invention;
fig. 8 is a flow chart of steps corresponding to the method of the present invention.
In the figure: 1. end plate, 2, first bipolar plate, 3, anodal electrolyte detects the chamber, 4, the negative pole electrolyte detects the chamber cavity, 5, ion exchange membrane, 6, anodal electrolyte import and export pipeline, 7, negative pole electrolyte import and export pipeline, 8, the insulation board, 801, first through-hole, 9, the reference detects the chamber, 10, the second bipolar plate, 1001, the cavity, 11, the second through-hole, 12, SOC detection device, 13, anodal electrolyte storage tank, 14, negative pole electrolyte storage tank, 15, the reference storage tank, 16, valve and pipeline.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In view of the many drawbacks of the prior art. Referring to fig. 8, the invention designs a method for monitoring the side reaction of an all-vanadium flow battery in real time, which is characterized by comprising the following steps: s1, acquiring sampling data, namely sampling potential parameters of the positive and negative electrolytes with different concentrations relative to a reference solution through an SOC detection device (when the potentials of the positive and negative electrolytes with different concentrations relative to the reference solution are measured, the concentrations of the positive and negative electrolytes need to consider the concentrations of 2, 3, 4 and 5-valent vanadium ions and hydrogen ions), and meanwhile, acquiring the total volume of the positive and negative electrolytes and the total volume of the negative electrolyte through a liquid level meter; the SOC detection device comprises an end plate, a first bipolar plate, a positive/negative electrolyte detection cavity, an ion exchange membrane, a positive electrolyte inlet/outlet pipeline and a negative electrolyte inlet/outlet pipeline which are respectively communicated with the positive/negative electrolyte detection cavity, a plurality of insulation plates provided with first through holes, a reference detection cavity and a second bipolar plate which is arranged in the reference detection cavity and used as a potential test electrode, wherein the insulation plates are respectively arranged on two sides of the ion exchange membrane to separate the reference detection cavity from the positive/negative electrolyte detection cavity; a reference solution is filled in the reference detection cavity; the electrolyte potential parameter comprises a system open circuit voltage;
s2, fitting an empirical formula of the positive/negative electrolyte potential through the sampling data; wherein the anode electrolyte potential empirical formula is
Figure BDA0001815634320000081
The potential empirical formula of the cathode electrolyte is
Figure BDA0001815634320000091
In the formula, EIs just、ENegative poleThe potential of the electrolyte of the positive electrode and the potential of the electrolyte of the negative electrode are respectively in mV;
Figure BDA0001815634320000092
Figure BDA0001815634320000093
the concentrations of the vanadium ions with valence of 2, 3, 4 and 5 are respectively; a. theIs justIs an empirical formula constant term of the positive electrode potential; b isIs justThe potential empirical formula of the positive electrode is the 4-valent vanadium ion coefficient; cIs justThe potential empirical formula of the positive electrode is the 5-valent vanadium ion coefficient; a. theNegative poleIs a constant term of an empirical formula of the cathode potential; b isNegative poleThe cathode potential empirical formula is the 2-valent vanadium ion coefficient; cNegative poleThe empirical formula of the potential of the negative electrode is the coefficient of the vanadium ions with the valence of 3;
s3, establishing an electrolyte concentration monitoring database and determining the concentration of each valence state vanadium ion in the positive/negative electrode electrolyte to be detected, wherein the electrolyte concentration monitoring database comprises at least one formula or inequality of a positive/negative electrode electrolyte potential empirical formula, a vanadium total mass conservation formula and a selectable formula/inequality, and the selectable formula/inequality comprises a system average valence state formula, a positive electrode vanadium total mass conservation formula, a negative electrode vanadium total mass conservation formula, a positive electrode vanadium concentration interval inequality and a negative electrode vanadium concentration interval inequality;
s4, calculating the total vanadium content of the positive/negative electrodes based on the determined concentration of each valence state vanadium ion in the positive/negative electrode electrolyte to be detected, and further obtaining the vanadium migration amount of the system;
s5, based on the calculated vanadium migration amount of the system, adjusting the electrolyte in the opposite direction of vanadium migration to restore the vanadium amount of the anode and the cathode to the initial optimal proportion so as to restore the system capacity;
wherein the vanadium migration amount calculation formula is as follows:
Figure BDA0001815634320000094
Figure BDA0001815634320000095
Figure BDA0001815634320000096
in the formula, NIs just、NNegative poleThe total amount of vanadium ions on the positive and negative sides respectively,
Figure BDA0001815634320000097
Figure BDA0001815634320000098
respectively the concentration of 2, 3, 4 and 5 valent vanadium ions, VIs just、VNegative poleRespectively the volume of the positive electrode electrolyte, the volume of the negative electrode electrolyte, NMigrationThe transfer amount of vanadium ions;
the adjustment strategy for adjusting the electrolyte in the direction opposite to the vanadium migration direction is as follows: if N is presentMigrationIf the electrolyte is positive, the electrolyte needs to be adjusted from the positive electrode to the negative electrode, and the adjustment volume is as follows:
Figure BDA0001815634320000101
if N is presentMigrationIs a negative value, thenElectrolyte needs to be adjusted from a negative electrode to a positive electrode, and the adjustment volume is as follows:
Figure BDA0001815634320000102
wherein the vanadium total mass conservation formula is
Figure BDA0001815634320000103
In the formula VIs just、VNegative poleRespectively the volume of the electrolyte of the positive electrode and the negative electrode, NGeneral assemblyThe unit is the total amount of vanadium ions in each valence state in the battery system and is mol;
formula of average valence state of said system
Figure BDA0001815634320000104
Wherein M is the average valence of vanadium ions in each valence state of the system;
the positive electrode vanadium total conservation formula
Figure BDA0001815634320000105
In the formula, NIs justThe unit mol is the total amount of vanadium ions on the positive electrode side;
the cathode vanadium total conservation formula;
Figure BDA0001815634320000106
in the formula, NNegative poleThe unit mol is the total amount of vanadium ions on the negative electrode side;
the positive electrode vanadium concentration interval inequality
Figure BDA0001815634320000107
In the formula, cInitial assemblyThe concentration value of the electrolyte initially added into the system;
the negative electrode vanadium concentration interval inequality
Figure BDA0001815634320000111
In the formula, cInitial assemblyIs the concentration value of the electrolyte initially charged into the system.
In an optional implementation mode, during data sampling, in a variation range of the composition of positive and negative electrolytes of the all-vanadium redox flow energy storage battery system, sampling is performed under the sampling condition that the variation interval of the concentrations of vanadium ions with different valence states is not more than 0.2mol/L, the total vanadium concentration sampling points of the positive and negative electrolytes are not less than 3, and the hydrogen ion concentration sampling points are not less than 3.
In an alternative embodiment, the detection cavity of the SOC detection device is formed by a combination of the following components: the device consists of a reference detection cavity and a positive electrolyte detection cavity; or the device consists of a reference detection cavity and a negative electrolyte detection cavity; or the reference detection cavity, the positive electrolyte detection cavity, the negative electrolyte detection cavity and the 3 electrolyte detection cavities.
In an alternative embodiment, the reference detection chamber is provided with a second through hole for the circulation and the renewal of the reference solution.
In an alternative embodiment, the reference solution is an electrolyte with vanadium ions. Preferably, the valence range of the vanadium ion in the electrolyte is any one of a valence range of 3.5 valence or a mixed valence range of 4 valence and 5 valence.
In an alternative embodiment, the part of the second bipolar plate, which is placed in the reference detection cavity, is provided with a cavity, the shape of the cavity is not limited, but the ratio of the area of the opening of the cavity to the total area of the electrodes in the reference detection cavity ranges from 0 to 1.
In an alternative embodiment, the material of the second bipolar plate is any one of a carbon material, a metal material, and a conductive polymer.
In an alternative embodiment, since the first through hole needs to be filled with a solution, the aperture of the first through hole is filled with a material with a high specific surface area or a hydrophilic material, preferably a carbon felt, activated carbon, or the like.
In an alternative embodiment, the first through hole is a through hole or a bent hole extending and bending along the thickness direction of the insulating plate to form a capillary structure, so that the reference detection chamber and the positive reference detection chamber and the negative reference detection chamber are connected through the capillary structure.
In an optional embodiment, the insulating plate is made of any one of a PP insulating material, a PE insulating material, a PVC insulating material, a PVDF insulating material, and a PTFE insulating material.
The invention further provides a flow battery system based on the SOC detection device.
The invention provides a system capable of monitoring the side reaction of the all-vanadium redox flow battery in real time, which is characterized by comprising the following components:
the data sampling unit is used for sampling potential parameters of the positive and negative electrolytes with different concentrations relative to a reference solution through the SOC detection device and simultaneously collecting the total volume of the positive electrolyte and the total volume of the negative electrolyte; the SOC detection device comprises an end plate, a first bipolar plate, a positive/negative electrolyte detection cavity, an ion exchange membrane, a positive electrolyte inlet/outlet pipeline and a negative electrolyte inlet/outlet pipeline which are respectively communicated with the positive/negative electrolyte detection cavity, a plurality of insulation plates provided with first through holes, a reference detection cavity and a second bipolar plate which is arranged in the reference detection cavity and used as a potential test electrode, wherein the insulation plates are respectively arranged on two sides of the ion exchange membrane to separate the reference detection cavity from the positive/negative electrolyte detection cavity; a reference solution is filled in the reference detection cavity;
the sampling data fitting unit is used for fitting an empirical formula of the potential of the positive/negative electrolyte through the sampling data acquired by the data sampling unit;
wherein the anode electrolyte potential empirical formula is
Figure BDA0001815634320000121
The potential empirical formula of the cathode electrolyte is
Figure BDA0001815634320000122
In the formula, EIs just、ENegative poleThe potential of the electrolyte of the positive electrode and the potential of the electrolyte of the negative electrode are respectively in mV;
Figure BDA0001815634320000123
Figure BDA0001815634320000124
the concentrations of the vanadium ions with valence of 2, 3, 4 and 5 are respectively; a. theIs justIs an empirical formula constant term of the positive electrode potential; b isIs justThe potential empirical formula of the positive electrode is the 4-valent vanadium ion coefficient; cIs justThe potential empirical formula of the positive electrode is the 5-valent vanadium ion coefficient; a. theNegative poleIs a constant term of an empirical formula of the cathode potential; b isNegative poleThe cathode potential empirical formula is the 2-valent vanadium ion coefficient; cNegative poleThe empirical formula of the potential of the negative electrode is the coefficient of the vanadium ions with the valence of 3;
the concentration monitoring unit is used for determining the concentration of each valence state vanadium ion in the positive/negative electrode electrolyte to be detected based on the established electrolyte concentration monitoring database, the electrolyte concentration monitoring database comprises at least one formula or inequality of a positive/negative electrode electrolyte potential empirical formula, a vanadium total mass conservation formula and a selectable formula/inequality, and the concentration of each valence state vanadium ion in the positive/negative electrode electrolyte to be detected is determined, wherein the selectable formula/inequality comprises a system average valence state formula, a positive electrode vanadium total mass conservation formula, a negative electrode vanadium total mass conservation formula, a positive electrode vanadium concentration interval inequality and a negative electrode vanadium concentration interval inequality;
wherein the vanadium total mass conservation formula is
Figure BDA0001815634320000131
In the formula VIs just、VNegative poleRespectively the volume of the electrolyte of the positive electrode and the negative electrode, NGeneral assemblyThe unit is the total amount of vanadium ions in each valence state in the battery system and is mol;
formula of average valence state of said system
Figure BDA0001815634320000132
Wherein M is the average valence of vanadium ions in each valence state of the system;
the positive electrode vanadium total conservation formula
Figure BDA0001815634320000133
In the formula, NIs justThe unit mol is the total amount of vanadium ions on the positive electrode side;
the cathode vanadium total conservation formula;
Figure BDA0001815634320000134
in the formula, NNegative poleThe unit mol is the total amount of vanadium ions on the negative electrode side;
the positive electrode vanadium concentration interval inequality
Figure BDA0001815634320000135
In the formula, cInitial assemblyThe concentration value of the electrolyte initially added into the system;
the negative electrode vanadium concentration interval inequality
Figure BDA0001815634320000136
In the formula, cInitial assemblyThe concentration value of the electrolyte initially added into the system;
the system vanadium migration amount calculation unit is used for calculating the total vanadium amount of the positive/negative electrodes based on the determined concentration of each valence vanadium ion in the positive/negative electrode electrolyte to be detected, so as to obtain the system vanadium migration amount;
and the capacity recovery unit is used for adjusting the electrolyte in the reverse direction of vanadium migration based on the calculated vanadium migration amount of the system so as to recover the vanadium amount of the anode and the cathode to the initial optimal proportion and recover the capacity of the system.
Wherein the vanadium migration amount calculation formula is as follows:
Figure BDA0001815634320000141
Figure BDA0001815634320000142
Figure BDA0001815634320000143
in the formula, NIs just、NNegative poleThe total amount of vanadium ions on the positive and negative sides respectively,
Figure BDA0001815634320000144
Figure BDA0001815634320000145
respectively the concentration of 2, 3, 4 and 5 valent vanadium ions, VIs just、VNegative poleRespectively the volume of the positive electrode electrolyte, the volume of the negative electrode electrolyte, NMigrationThe transfer amount of vanadium ions;
the adjustment strategy for adjusting the electrolyte in the direction opposite to the vanadium migration direction is as follows: if N is presentMigrationIf the electrolyte is positive, the electrolyte needs to be adjusted from the positive electrode to the negative electrode, and the adjustment volume is as follows:
Figure BDA0001815634320000146
if N is presentMigrationIf the electrolyte is a negative value, the electrolyte needs to be adjusted from the negative electrode to the positive electrode, and the adjustment volume is as follows:
Figure BDA0001815634320000147
furthermore, when data sampling is carried out, in the variation range of the composition of the positive and negative electrolytes of the all-vanadium redox flow energy storage battery system, sampling is carried out under the condition that the variation interval of the vanadium ion concentration of different valence states is not more than 0.2mol/L, the total vanadium concentration sampling points of the positive and negative electrolytes are not less than 3, and the hydrogen ion concentration sampling points are not less than 3.
Based on the above design scheme, the embodiment shown in fig. 1 to 5 is taken as an example for further explanation and demonstration, and the detection cavity of the SOC detection device 12 adopted in this example is composed of a reference detection cavity, a positive electrolyte detection cavity, a negative electrolyte detection cavity and 3 electrolyte detection cavities; specifically, as shown in fig. 1, the SOC detection device for detecting the state of the electrolyte in the flow cell includes an end plate 1, a first bipolar plate 2, a positive electrolyte detection cavity 3, a negative electrolyte detection cavity 4, an ion exchange membrane 5, a positive electrolyte inlet and outlet pipeline 6 (connected to a positive electrolyte storage tank 13) and a negative electrolyte inlet and outlet pipeline 7 (connected to a negative electrolyte storage tank 14) respectively communicated with the positive/negative electrolyte detection cavities; 4 insulating plates 8 provided with first through holes 801, a reference detection cavity 9 provided with second through holes 11 for allowing a reference solution to circulate and update, and a second bipolar plate 10 arranged in the reference detection cavity and used as a potential test electrode, wherein the insulating plates 9 are respectively arranged at two sides of the ion exchange membrane 5 to separate the reference detection cavity 9 from the positive/negative electrolyte detection cavity (i.e. the positive electrolyte detection cavity and/or the negative electrolyte detection cavity are/is separated from the reference cavity by an ionic membrane and the insulating plates); the reference detection cavity is filled with a reference solution.
The reference solution is an electrolyte containing vanadium ions, and the valence state of the vanadium ions is in a mixed valence state of 4 valence and 5 valence; the part of the second bipolar plate, which is arranged in the reference detection cavity, is provided with a square cavity 1001 as shown in fig. 2, or a structure as shown in fig. 3; the second bipolar plate is made of a carbon material; the aperture of the first through hole is filled with a carbon felt material; as shown in fig. 4, the first through hole is a capillary structure (the longer the length of the opening is, the better); the insulating plate is made of a PVC insulating material; as shown in fig. 5, the reference detection chamber is provided with a second through hole for communicating and updating the reference solution, and the reference solution is sent from the reference storage tank 15 to the reference detection chamber through the second through hole by a valve and a pipeline 16;
wherein the positive/negative electrolyte potential empirical formula;
wherein the anode electrolyte potential empirical formula is
Figure BDA0001815634320000151
The potential empirical formula of the cathode electrolyte is
Figure BDA0001815634320000152
In the formula, EIs just、ENegative poleThe potentials of the positive electrolyte and the negative electrolyte are respectively in mV;
Figure BDA0001815634320000153
Figure BDA0001815634320000154
the concentrations of the vanadium ions with valence of 2, 3, 4 and 5 are respectively; a. theIs justAn empirical formula constant term of the positive electrode potential, wherein the optimal value is 695.4; b isIs justThe potential empirical formula of the positive electrode is the vanadium ion coefficient with the valence of 4, and the preferred value is-19.1; cIs justThe potential of the positive electrode has an empirical formula of a 5-valent vanadium ion coefficient, and the optimal value is 165.2; a. theNegative poleThe preferred value of the constant term of the negative electrode potential empirical formula is-746.8; b isNegative poleThe cathode potential empirical formula 2 is the vanadium ion coefficient with the optimal value of-65.9;Cnegative poleThe potential empirical formula of the negative electrode is the coefficient of the vanadium ion with the valence of 3, and the optimal value is 129.5;
at last, at least four equations or inequalities including the formulas (i), (ii) and (iii) and (iv) -are selected to be combined, and the equation set is solved to obtain the concentration of each valence state vanadium ion in the positive and negative electrolyte;
s4, calculating the total vanadium content of the positive/negative electrodes based on the determined concentration of each valence state vanadium ion in the positive/negative electrode electrolyte to be detected, and further obtaining the vanadium migration amount of the system;
and S5, adjusting the electrolyte in the reverse direction of vanadium migration based on the calculated vanadium migration amount of the system to restore the vanadium amount of the anode and the cathode to the initial optimal proportion so as to restore the system capacity.
Wherein the vanadium migration amount calculation formula is as follows:
Figure BDA0001815634320000161
Figure BDA0001815634320000162
Figure BDA0001815634320000163
in the formula, NIs just、NNegative poleThe total amount of vanadium ions on the positive and negative sides respectively,
Figure BDA0001815634320000164
Figure BDA0001815634320000165
respectively the concentration of 2, 3, 4 and 5 valent vanadium ions, VIs just、VNegative poleRespectively the volume of the positive electrode electrolyte, the volume of the negative electrode electrolyte, NMigrationThe transfer amount of vanadium ions;
the adjustment strategy for adjusting the electrolyte in the direction opposite to the vanadium migration direction is as follows: if N is presentMigrationIf the value is positive, the voltage is adjusted from positive to negativeElectrolyte, the adjustment volume is:
Figure BDA0001815634320000166
if N is presentMigrationIf the electrolyte is a negative value, the electrolyte needs to be adjusted from the negative electrode to the positive electrode, and the adjustment volume is as follows:
Figure BDA0001815634320000167
see examples 1, 2 for specific calculation examples:
example 1
Potential, volume and calculated vanadium concentration monitored by system of table 12 kW
Figure BDA0001815634320000168
Positive and negative total vanadium content NIs just＝37.4*1.605＝60.027mol，NNegative pole42.6 × 1.560 ═ 66.456mol of total vanadium migrates to the negative electrode, and the volume of the electrolyte needs to be adjusted to the positive electrode if the total vanadium content of the positive electrode and the negative electrode of the system is equal
Figure BDA0001815634320000171
The system discharge capacity before and after the electrolyte is adjusted from the negative electrode to the positive electrode is shown in fig. 6, and it can be seen that the system capacity is recovered by the adjustment.
Example 2
Potential, volume and calculated vanadium concentration monitored by system of table 12 kW
Figure BDA0001815634320000172
Positive and negative total vanadium content NIs just＝43.2*1.605＝69.336mol，NNegative pole36.8 × 1.604 mol 59.027mol of total vanadium to positive electrodeMigration, if the total vanadium content of the anode and the cathode is equal to the initial vanadium content of the system, the volume of the electrolyte needs to be adjusted to the cathode
Figure BDA0001815634320000173
The system discharge capacity before and after the electrolyte is adjusted from the positive electrode to the negative electrode is shown in fig. 7, and it can be seen that the system capacity is recovered by the adjustment.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (5)

1.一种用于实时监测全钒液流电池钒迁移的方法，其特征在于，包括如下步骤：1. a method for real-time monitoring vanadium migration of all-vanadium redox flow battery, is characterized in that, comprises the steps: S1、获取采样数据，即通过SOC检测装置对不同浓度的正负极电解液相对于参比溶液的电位参数进行采样，同时对正极电解液总体积、负极电解液总体积进行采集；所述SOC检测装置包括端板、第一双极板、正/负极电解液检测腔、离子交换膜、分别与所述正/负极电解液检测腔相连通的正极电解液进出口管路与负极电解液进出口管路，多个开设有第一通孔的绝缘板、参比检测腔以及置于所述参比检测腔作为电位测试电极的第二双极板，其中，所述绝缘板被分别设置于所述离子交换膜两侧以间隔参比检测腔与正/负极电解液检测腔；所述参比检测腔内充有参比溶液；所述参比检测腔开有供参比溶液流通更新的第二通孔；所述第二双极板置于参比检测腔内部分开有空腔，所述空腔的开孔面积与参比检测腔腔体内电极总面积的比例范围为0～1；所述第一通孔为直通孔或者沿所述绝缘板厚度方向延伸弯折的弯折孔；S1. Obtain sampling data, that is, sampling the potential parameters of positive and negative electrolytes with different concentrations relative to the reference solution through the SOC detection device, and simultaneously collect the total volume of the positive electrolyte and the total volume of the negative electrolyte; the SOC The detection device includes an end plate, a first bipolar plate, a positive/negative electrolyte detection chamber, an ion exchange membrane, a positive electrolyte inlet and outlet pipelines that are respectively communicated with the positive/negative electrolyte detection chamber and a negative electrolyte inlet and outlet. The outlet pipeline, a plurality of insulating plates with first through holes, a reference detection chamber, and a second bipolar plate placed in the reference detection chamber as a potential test electrode, wherein the insulating plates are respectively arranged on Both sides of the ion exchange membrane are spaced with a reference detection chamber and a positive/negative electrode electrolyte detection chamber; the reference detection chamber is filled with a reference solution; a second through hole; the second bipolar plate is placed inside the reference detection cavity and is divided into a cavity, and the ratio of the opening area of the cavity to the total area of the electrodes in the reference detection cavity is in the range of 0 to 1; The first through hole is a straight through hole or a bending hole extending and bending along the thickness direction of the insulating plate; S2、通过采样数据拟合出正/负极电解液电位经验公式；S2. Fit the positive/negative electrolyte potential empirical formula by sampling data; 其中，所述正极电解液电位经验公式为Wherein, the empirical formula for the potential of the positive electrode electrolyte is:
Figure FDA0003258698910000011
Figure FDA0003258698910000011
 所述负极电解液电位经验公式为The negative electrode electrolyte potential empirical formula is
Figure FDA0003258698910000012
Figure FDA0003258698910000012
 式中，E正、E负分别为正、负极电解液电位，单位mV；
Figure FDA0003258698910000013
Figure FDA0003258698910000014
分别为2价、3价、4价、5价钒离子浓度；A正为正极电位经验公式常数项；B正为正极电位经验公式4价钒离子系数；C正为正极电位经验公式5价钒离子系数；A负为负极电位经验公式常数项；B负为负极电位经验公式2价钒离子系数；C负为负极电位经验公式3价钒离子系数；In the formula, E positive and E negative are the positive and negative electrolyte potentials, respectively, in mV;
Figure FDA0003258698910000013
Figure FDA0003258698910000014
are the vanadium ion concentrations of 2, 3, 4 and 5, respectively; A is the constant term of the positive electrode potential empirical formula; B is the 4-valent vanadium ion coefficient of the positive potential empirical formula; C is the 5-valent vanadium of the positive potential empirical formula Ion coefficient; A negative is the negative electrode potential empirical formula constant term; B negative is the negative electrode potential empirical formula bivalent vanadium ion coefficient; C negative is the negative electrode potential empirical formula trivalent vanadium ion coefficient; S3、建立电解液浓度监测数据库并确定待测正/负极电解液中各个价态钒离子浓度，所述电解液浓度监测数据库包括正/负极电解液电位经验公式、钒总物质量守恒公式以及可选公式/不等式中的至少一个公式或者不等式，所述可选公式/不等式包括系统平均价态公式、正极钒总量守恒公式、负极钒总量守恒公式、正极钒浓度区间不等式以及负极钒浓度区间不等式；S3, establish an electrolyte concentration monitoring database and determine the concentration of each valence vanadium ion in the positive/negative electrode electrolyte to be tested, and the electrolyte concentration monitoring database includes positive/negative electrode electrolyte potential empirical formula, total vanadium mass conservation formula and possible Select at least one formula or inequality among the formulas/inequalities, the optional formulas/inequalities include the system average valence formula, the total amount of positive vanadium conservation formula, the negative electrode total amount of vanadium conservation formula, the positive electrode vanadium concentration interval inequality and the negative electrode vanadium concentration interval inequality; S4、基于所确定的待测正/负极电解液中各个价态钒离子浓度，计算出正/负极总钒量，进而得出系统钒迁移量；S4, based on the determined concentration of each valence vanadium ion in the positive/negative electrode electrolyte to be tested, calculate the positive/negative electrode total vanadium amount, and then obtain the system vanadium migration amount; S5、基于所计算的系统钒迁移量，向钒迁移的反方向调整电解液使正负极钒量恢复到初始最佳比例使得系统容量得到恢复；S5. Based on the calculated system vanadium migration amount, adjust the electrolyte in the opposite direction of vanadium migration to restore the positive and negative vanadium amounts to the initial optimum ratio so that the system capacity is restored; 其中，钒迁移量计算公式如下：Among them, the calculation formula of vanadium migration is as follows:
Figure FDA0003258698910000021
Figure FDA0003258698910000021
Figure FDA0003258698910000022
Figure FDA0003258698910000022
Figure FDA0003258698910000023
Figure FDA0003258698910000023
 式中，N正、N负分别为正负极侧钒离子总物质的量，
Figure FDA0003258698910000024
Figure FDA0003258698910000025
分别为2、3、4、5价钒离子浓度，V正、V负分别为正极电解液体积、负极电解液体积，N迁移为钒离子迁移量；In the formula, N positive and N negative are the total amount of vanadium ions on the positive and negative sides, respectively,
Figure FDA0003258698910000024
Figure FDA0003258698910000025
are the concentrations of 2, 3, 4, and 5 valent vanadium ions, respectively, V positive and V negative are the volume of positive electrolyte and negative electrolyte, respectively, and N migration is the amount of vanadium ion migration; 向钒迁移的反方向调整电解液的调整策略为：若N迁移为正值，则需由正极向负极调整电解液，调整体积为：The adjustment strategy for adjusting the electrolyte in the opposite direction of vanadium migration is: if the N migration is positive, the electrolyte needs to be adjusted from the positive electrode to the negative electrode, and the adjusted volume is:
Figure FDA0003258698910000026
Figure FDA0003258698910000026
 若N迁移为负值，则需由负极向正极调整电解液，调整体积为：If the N migration is negative, the electrolyte needs to be adjusted from the negative electrode to the positive electrode, and the adjusted volume is:
Figure FDA0003258698910000027
Figure FDA0003258698910000027
 其中，所述钒总物质量守恒公式为Wherein, the formula for the conservation of the total mass of vanadium is:
Figure FDA0003258698910000028
Figure FDA0003258698910000028
 式中V正、V负分别为正、负极电解液体积，N总为电池系统内各价态钒离子的总物质的量，单位为mol；In the formula, V is positive and V is negative , respectively, the volume of positive and negative electrolytes, and N is the total amount of vanadium ions in each valence state in the battery system, and the unit is mol; 所述系统平均价态公式The system average valence formula
Figure FDA0003258698910000029
Figure FDA0003258698910000029
 式中，M为系统各价态钒离子的平均价态；In the formula, M is the average valence state of each valence state vanadium ion in the system; 所述正极钒总量守恒公式The formula for the conservation of the total amount of vanadium in the cathode
Figure FDA0003258698910000031
Figure FDA0003258698910000031
 式中，N正为正极侧钒离子总物质的量，单位mol；In the formula, N is the total amount of vanadium ions on the positive side, in mol; 所述负极钒总量守恒公式；The formula for the conservation of the total amount of vanadium in the negative electrode;
Figure FDA0003258698910000032
Figure FDA0003258698910000032
 式中，N负为负极侧钒离子总物质的量，单位mol；In the formula, N negative is the total amount of vanadium ions on the negative side, in mol; 所述正极钒浓度区间不等式The anode vanadium concentration interval inequality
Figure FDA0003258698910000033
Figure FDA0003258698910000033
 式中，c初始总为初始加入系统内的电解液浓度值；In the formula, c is the initial value of the electrolyte concentration initially added to the system; 所述负极钒浓度区间不等式The negative electrode vanadium concentration interval inequality
Figure FDA0003258698910000034
Figure FDA0003258698910000034
 式中，c初始总为初始加入系统内的电解液浓度值。In the formula, c is the initial value of the electrolyte concentration initially added to the system. 2.根据权利要求1所述的一种用于实时监测全钒液流电池钒迁移的方法，其特征在于：2. a kind of method for real-time monitoring vanadium migration of all-vanadium redox flow battery according to claim 1, is characterized in that: 在进行数据采样时，在全钒液流储能电池系统正负极电解液组成变化范围内，以不同价态钒离子浓度变化间隔不大于0.2mol/L，正负极电解液总钒浓度取样点不少于3个，氢离子浓度取样点不少于3个为采样条件进行采样。During data sampling, within the range of the composition of the positive and negative electrolytes of the all-vanadium redox flow energy storage battery system, the variation interval of the concentration of vanadium ions in different valence states is not greater than 0.2mol/L, and the total vanadium concentration of the positive and negative electrolytes is sampled. No less than 3 points, and no less than 3 sampling points for hydrogen ion concentration are sampling conditions. 3.根据权利要求1所述的一种用于实时监测全钒液流电池钒迁移的方法，其特征在于：3. a kind of method for real-time monitoring vanadium migration of all-vanadium redox flow battery according to claim 1, is characterized in that: 所述参比溶液为具有钒离子的电解液。The reference solution is an electrolyte with vanadium ions. 4.一种用于实时监测全钒液流电池钒迁移的系统，其特征在于，包括：4. a system for real-time monitoring of vanadium migration in an all-vanadium redox flow battery, is characterized in that, comprising: 数据采样单元，用于通过SOC检测装置对不同浓度的正负极电解液相对于参比溶液的电位参数进行采样，同时对正极电解液总体积、负极电解液总体积进行采集；所述SOC检测装置包括端板、第一双极板、正/负极电解液检测腔、离子交换膜、分别与所述正/负极电解液检测腔相连通的正极电解液进出口管路与负极电解液进出口管路，多个开设有第一通孔的绝缘板、参比检测腔以及置于所述参比检测腔作为电位测试电极的第二双极板，其中，所述绝缘板被分别设置于所述离子交换膜两侧以间隔参比检测腔与正/负极电解液检测腔；所述参比检测腔内充有参比溶液；The data sampling unit is used to sample the potential parameters of the positive and negative electrolytes with different concentrations relative to the reference solution through the SOC detection device, and simultaneously collect the total volume of the positive electrolyte and the total volume of the negative electrolyte; the SOC detection The device includes an end plate, a first bipolar plate, a positive/negative electrode electrolyte detection chamber, an ion exchange membrane, a positive electrode electrolyte inlet and outlet pipelines and a negative electrode electrolyte inlet and outlet that are respectively communicated with the positive/negative electrode electrolyte detection chambers. pipeline, a plurality of insulating plates with first through holes, a reference detection chamber, and a second bipolar plate placed in the reference detection chamber as a potential test electrode, wherein the insulating plates are respectively arranged in the The two sides of the ion exchange membrane are spaced with a reference detection chamber and a positive/negative electrode electrolyte detection chamber; the reference detection chamber is filled with a reference solution; 采样数据拟合单元，用于通过数据采样单元所获取的采样数据拟合出正/负极电解液电位经验公式；The sampling data fitting unit is used for fitting the positive/negative electrolyte potential empirical formula through the sampling data obtained by the data sampling unit; 其中，所述正极电解液电位经验公式为Wherein, the empirical formula for the potential of the positive electrode electrolyte is:
Figure FDA0003258698910000041
Figure FDA0003258698910000041
 所述负极电解液电位经验公式为The negative electrode electrolyte potential empirical formula is
Figure FDA0003258698910000042
Figure FDA0003258698910000042
 式中，E正、E负分别为正负极电解液电位，单位mV；
Figure FDA0003258698910000043
Figure FDA0003258698910000044
分别为2价、3价、4价、5价钒离子浓度；A正为正极电位经验公式常数项；B正为正极电位经验公式4价钒离子系数；C正为正极电位经验公式5价钒离子系数；A负为负极电位经验公式常数项；B负为负极电位经验公式2价钒离子系数；C负为负极电位经验公式3价钒离子系数；In the formula, E positive and E negative are the positive and negative electrolyte potentials, respectively, in mV;
Figure FDA0003258698910000043
Figure FDA0003258698910000044
are the vanadium ion concentrations of 2, 3, 4, and 5, respectively; A is the constant term of the positive electrode potential empirical formula; B is the tetravalent vanadium ion coefficient of the positive electrode potential empirical formula; C is the 5-valent vanadium of the positive electrode potential empirical formula Ion coefficient; A negative is the negative electrode potential empirical formula constant term; B negative is the negative electrode potential empirical formula bivalent vanadium ion coefficient; C negative is the negative electrode potential empirical formula trivalent vanadium ion coefficient; 浓度监测单元，用于基于所建立的电解液浓度监测数据库确定待测正/负极电解液中各个价态钒离子浓度，所述电解液浓度监测数据库包括正/负极电解液电位经验公式、钒总物质量守恒公式以及可选公式/不等式中的至少一个公式或者不等式确定待测正/负极电解液中各个价态钒离子浓度，所述可选公式/不等式包括系统平均价态公式、正极钒总量守恒公式、负极钒总量守恒公式、正极钒浓度区间不等式以及负极钒浓度区间不等式；The concentration monitoring unit is used to determine the concentration of each valence vanadium ion in the positive/negative electrode electrolyte to be tested based on the established electrolyte concentration monitoring database, where the electrolyte concentration monitoring database includes positive/negative electrode electrolyte potential empirical formula, total vanadium The mass conservation formula and at least one formula or inequality in the optional formula/inequalities to determine the concentration of vanadium ions in each valence state in the positive/negative electrode electrolyte to be tested, the optional formulas/inequalities include the system average valence state formula, the total positive electrode vanadium Conservation formula, total amount of anode vanadium conservation formula, anode vanadium concentration interval inequality and anode vanadium concentration interval inequality; 系统钒迁移量计算单元，用于基于所确定的待测正/负极电解液中各个价态钒离子浓度，计算出正/负极总钒量，进而得出系统钒迁移量；The system vanadium migration amount calculation unit is used to calculate the positive/negative electrode total vanadium amount based on the determined concentration of each valence vanadium ion in the positive/negative electrode electrolyte to be tested, and then obtain the system vanadium migration amount; 容量恢复单元，用于基于所计算的系统钒迁移量，向钒迁移的反方向调整电解液使正负极钒量恢复到初始最佳比例使得系统容量得到恢复。The capacity recovery unit is used to adjust the electrolyte in the opposite direction of vanadium migration based on the calculated system vanadium migration amount to restore the positive and negative vanadium amounts to the initial optimum ratio so that the system capacity is restored. 5.根据权利要求4所述的用于实时监测全钒液流电池钒迁移的系统，其特征在于：5. the system for monitoring vanadium migration of all-vanadium redox flow battery in real time according to claim 4, is characterized in that: 其中，钒迁移量计算公式如下：Among them, the calculation formula of vanadium migration is as follows:
Figure FDA0003258698910000051
Figure FDA0003258698910000051
Figure FDA0003258698910000052
Figure FDA0003258698910000052
Figure FDA0003258698910000053
Figure FDA0003258698910000053
 式中，N正、N负分别为正负极侧钒离子总物质的量，
Figure FDA0003258698910000054
Figure FDA0003258698910000055
分别为2、3、4、5价钒离子浓度，V正、V负分别为正极电解液体积、负极电解液体积，N迁移为钒离子迁移量；In the formula, N positive and N negative are the total amount of vanadium ions on the positive and negative sides, respectively,
Figure FDA0003258698910000054
Figure FDA0003258698910000055
are the concentrations of 2, 3, 4, and 5 valent vanadium ions, respectively, V positive and V negative are the volume of positive electrolyte and negative electrolyte, respectively, and N migration is the amount of vanadium ion migration; 向钒迁移的反方向调整电解液的调整策略为：若N迁移为正值，则需由正极向负极调整电解液，调整体积为：The adjustment strategy for adjusting the electrolyte in the opposite direction of vanadium migration is: if the N migration is positive, the electrolyte needs to be adjusted from the positive electrode to the negative electrode, and the adjusted volume is:
Figure FDA0003258698910000056
Figure FDA0003258698910000056
 若N迁移为负值，则需由负极向正极调整电解液，调整体积为：If the N migration is negative, the electrolyte needs to be adjusted from the negative electrode to the positive electrode, and the adjusted volume is:
Figure FDA0003258698910000057
Figure FDA0003258698910000057
 其中，所述钒总物质量守恒公式为Wherein, the formula for the conservation of the total mass of vanadium is:
Figure FDA0003258698910000058
Figure FDA0003258698910000058
 式中V正、V负分别为正、负极电解液体积，N总为电池系统内各价态钒离子的总物质的量，单位为mol；In the formula, V is positive and V is negative , respectively, the volume of positive and negative electrolytes, and N is the total amount of vanadium ions in each valence state in the battery system, and the unit is mol; 所述系统平均价态公式The system average valence formula
Figure FDA0003258698910000059
Figure FDA0003258698910000059
 式中，M为系统各价态钒离子的平均价态；In the formula, M is the average valence state of each valence state vanadium ion in the system; 所述正极钒总量守恒公式The formula for the conservation of the total amount of vanadium in the cathode
Figure FDA00032586989100000510
Figure FDA00032586989100000510
 式中，N正为正极侧钒离子总物质的量，单位mol；In the formula, N is the total amount of vanadium ions on the positive side, in mol; 所述负极钒总量守恒公式；The formula for the conservation of the total amount of vanadium in the negative electrode;
Figure FDA0003258698910000061
Figure FDA0003258698910000061
 式中，N负为负极侧钒离子总物质的量，单位mol；In the formula, N negative is the total amount of vanadium ions on the negative side, in mol; 所述正极钒浓度区间不等式The anode vanadium concentration interval inequality
Figure FDA0003258698910000062
Figure FDA0003258698910000062
 式中，c初始总为初始加入系统内的电解液浓度值；In the formula, c is the initial value of the electrolyte concentration initially added to the system; 所述负极钒浓度区间不等式The negative electrode vanadium concentration interval inequality
Figure FDA0003258698910000063
Figure FDA0003258698910000063
 式中，c初始总为初始加入系统内的电解液浓度值。In the formula, c is the initial value of the electrolyte concentration initially added to the system.
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