CN109473703B - Method and system for monitoring electrolyte concentration of all-vanadium redox flow battery in real time - Google Patents

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

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CN109473703B
CN109473703B CN201811140260.3A CN201811140260A CN109473703B CN 109473703 B CN109473703 B CN 109473703B CN 201811140260 A CN201811140260 A CN 201811140260A CN 109473703 B CN109473703 B CN 109473703B
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赵叶龙
董艳影
于彩红
孙恺
邹毅
宋玉波
刘宗浩
王良
梁加富
高新亮
王丹
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Abstract

The invention discloses a method and a system for monitoring the electrolyte concentration of an all-vanadium redox flow battery in real time, wherein the method comprises the following steps: 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; fitting an empirical formula of the potential of the positive/negative electrolyte through sampling data; and establishing an electrolyte concentration monitoring database, wherein the database comprises an anode/cathode electrolyte potential empirical formula, a vanadium total mass conservation formula and at least one formula or inequality in optional formulas/inequalities to determine the concentration of each valence-state vanadium ion in the anode/cathode electrolyte to be detected. The method can monitor the concentration of the positive/negative vanadium ions in the all-vanadium redox flow battery system in real time, and provides accurate and timely data support for formulating a system control strategy.

Description

Method and system for monitoring electrolyte concentration 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 the concentration of electrolyte of an all-vanadium flow battery in real time.
Background
The online monitoring method for the concentration of the electrolyte of the flow battery in the prior art has the following problems:
1. although a potentiometric titration method or a spectrophotometric method is adopted to analyze the composition and the state of the electrolyte, relatively accurate results can be obtained, but the biggest problem is that the state of the electrolyte cannot be monitored on site in real time, and the solution needs to be taken out and then measured, namely, the methods are all offline sampling analysis and cannot or are difficult to realize online analysis;
2. an equation simultaneous method, for example, CN 20151072457 solves various ion concentrations simultaneously through an electrolyte refractive index, a standard nernst equation, and equations such as total vanadium conservation and positive charge conservation, but the concentration of various ions cannot be accurately calculated by using the nernst equation, and variables in the equation are the activities of various ions;
in summary, the existing methods for monitoring the concentration state of the electrolyte of the flow battery on line have certain disadvantages, 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 the electrolyte concentration 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 the electrolyte concentration 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 GDA0003244529400000021
The potential empirical formula of the cathode electrolyte is
Figure GDA0003244529400000022
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 GDA0003244529400000023
Figure GDA0003244529400000024
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 justIs a positive electrode potentialEmpirical formula 5 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 a positive/negative electrode electrolyte potential empirical formula, a vanadium total mass conservation formula and at least one formula or inequality of selectable formulas/inequalities to determine the concentration of each valence state vanadium ion in the positive/negative electrode electrolyte to be detected, and the selectable formulas/inequalities comprise 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 GDA0003244529400000025
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 GDA0003244529400000026
Wherein M is the average valence of vanadium ions in each valence state of the system;
the positive electrode vanadium total conservation formula
Figure GDA0003244529400000031
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 GDA0003244529400000032
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 GDA0003244529400000033
In the formula, cInitial assemblyThe concentration value of the electrolyte initially added into the system;
the negative electrode vanadium concentration interval inequality
Figure GDA0003244529400000034
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 flow battery system capable of monitoring the electrolyte concentration of an all-vanadium 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 GDA0003244529400000041
The potential empirical formula of the cathode electrolyte is
Figure GDA0003244529400000042
In the formula, EIs just、ENegative poleThe potentials of the positive electrolyte and the negative electrolyte are respectively in mV;
Figure GDA0003244529400000043
Figure GDA0003244529400000044
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 a positive/negative electrode electrolyte potential empirical formula, a vanadium total mass conservation formula and at least one formula or inequality of selectable formulas/inequalities so as to determine the concentration of each valence state vanadium ion in the positive/negative electrode electrolyte to be detected, and the selectable formulas/inequalities comprise 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 GDA0003244529400000051
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 GDA0003244529400000052
Wherein M is the average valence of vanadium ions in each valence state of the system;
the positive electrode vanadium total conservation formula
Figure GDA0003244529400000053
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 GDA0003244529400000054
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 GDA0003244529400000055
In the formula, cInitial assemblyThe concentration value of the electrolyte initially added into the system;
the negative electrode vanadium concentration interval inequality
Figure GDA0003244529400000056
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 ion composition of the positive and negative electrolytes can be calculated by only acquiring the positive and negative electrolyte volumes of the system and the potential difference of the positive and negative electrolytes relative to the reference solution, so that the vanadium ion concentration of the positive and negative electrodes in the all-vanadium redox flow battery system can be monitored in real time, and accurate and timely data support is provided for formulating a system control strategy.
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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;
FIG. 6 is a flow chart illustrating the steps of the method of the present invention.
In the figure: 1. end plate, 2, first bipolar plate, 3, anodal electrolyte detects the chamber, 4, 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, reference detection chamber, 10, the second bipolar plate, 1001, the cavity, 11, the second through-hole, 13, anodal electrolyte storage tank, 14, negative pole electrolyte storage tank, 15, 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. 6, the invention designs a method for monitoring the electrolyte concentration of an all-vanadium redox 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 for calculating the positive/negative electrolyte potential through sampling data; wherein the anode electrolyte potential empirical formula is
Figure GDA0003244529400000071
The potential empirical formula of the cathode electrolyte is
Figure GDA0003244529400000072
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 GDA0003244529400000073
Figure GDA0003244529400000074
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 based on the database, 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;
wherein the vanadium total mass conservation formula is
Figure GDA0003244529400000081
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 GDA0003244529400000082
Wherein M is the average valence of vanadium ions in each valence state of the system;
the positive electrode vanadium total conservation formula
Figure GDA0003244529400000083
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 GDA0003244529400000084
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 GDA0003244529400000085
In the formula, cInitial assemblyThe concentration value of the electrolyte initially added into the system;
the negative electrode vanadium concentration interval inequality
Figure GDA0003244529400000086
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 flow battery system capable of monitoring the electrolyte concentration of an all-vanadium 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 GDA0003244529400000101
The potential empirical formula of the cathode electrolyte is
Figure GDA0003244529400000102
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 GDA0003244529400000103
Figure GDA0003244529400000104
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 GDA0003244529400000105
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 GDA0003244529400000111
Wherein M is the average valence of vanadium ions in each valence state of the system;
the positive electrode vanadium total conservation formula
Figure GDA0003244529400000112
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 GDA0003244529400000113
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 GDA0003244529400000114
In the formula, cInitial assemblyThe concentration value of the electrolyte initially added into the system;
the negative electrode vanadium concentration interval inequality
Figure GDA0003244529400000115
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.
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 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 GDA0003244529400000121
The potential empirical formula of the cathode electrolyte is
Figure GDA0003244529400000122
In the formula, EIs just、ENegative poleThe potentials of the positive electrolyte and the negative electrolyte are respectively in mV;
Figure GDA0003244529400000123
Figure GDA0003244529400000124
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;
see the following table for specific calculation examples
Figure GDA0003244529400000131
Figure GDA0003244529400000141
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 (4)

1. A method for monitoring the electrolyte concentration 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 FDA0003244529390000011
The potential empirical formula of the cathode electrolyte is
Figure FDA0003244529390000013
Wherein E isIs just、ENegative pole
The potential of the electrolyte of the anode and the cathode respectively is in mV unit;
Figure FDA0003244529390000014
Figure FDA0003244529390000015
the concentrations of the vanadium ions with valence of 2, 3, 4 and 5 are respectively; a. theIs justThe positive electrode potential empirical formula constant term is 695.4; b isIs justThe potential empirical formula of the positive electrode shows that the coefficient of the 4-valent vanadium ion is-19.1; cIs justThe potential empirical formula of the positive electrode shows that the coefficient of the vanadium ion with the valence of 5 is 165.2; a. theNegative poleThe constant term of the negative electrode potential empirical formula is-746.8; b isNegative poleThe cathode potential empirical formula 2 valence vanadium ion coefficient is-65.9; cNegative poleThe potential empirical formula of the negative electrode shows that the coefficient of the vanadium ion with valence 3 is 129.5;
s3, establishing an electrolyte concentration monitoring database and determining the concentration of each valence state vanadium ion in the anode electrolyte and the cathode electrolyte to be detected, wherein the electrolyte concentration monitoring database comprises an anode electrolyte potential empirical formula, a cathode electrolyte potential empirical formula, a vanadium total substance quantity conservation formula and at least one optional formula in optional formulas, and the optional formulas comprise a system average valence state formula, an anode vanadium total quantity conservation formula and a cathode vanadium total quantity conservation formula; or the electrolyte concentration monitoring database comprises an anode electrolyte potential empirical formula, a cathode electrolyte potential empirical formula, a vanadium total substance quantity conservation formula, an anode vanadium concentration interval inequality and a cathode vanadium concentration interval inequality;
the quantity conservation formula of the vanadium total substance is
Figure FDA0003244529390000021
In the formula VIs just、VNegative poleRespectively the volumes of the positive and negative electrolytes, 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 FDA0003244529390000022
Wherein M is the average valence of vanadium ions in each valence state of the system;
the positive electrode vanadium total conservation formula
Figure FDA0003244529390000023
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 FDA0003244529390000025
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 FDA0003244529390000024
In the formula, cInitial assemblyThe concentration value of the electrolyte initially added into the system;
the negative electrode vanadium concentration interval inequality
Figure FDA0003244529390000026
In the formula, cInitial assemblyThe concentration value of the electrolyte initially added into the system;
the reference detection cavity is provided with a second through hole for the circulation and the updating of a reference solution; the reference solution is an electrolyte with vanadium ions;
the second bipolar plate is arranged in the reference detection cavity, a cavity is formed in the part, arranged 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;
the aperture of the first through hole is filled with carbon felt or activated carbon;
the first through hole is a straight through hole or a bent hole extending and bending along the thickness direction of the insulating plate.
2. The method for monitoring the electrolyte concentration of the all-vanadium flow battery in real time according to claim 1, wherein the method comprises the following steps:
when data sampling is carried out, sampling is carried out 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 and the total vanadium concentration sampling points of the positive electrolyte and the negative electrolyte are not less than 3 in the variation range of the composition of the positive electrolyte and the negative electrolyte of the all-vanadium redox flow energy storage battery system.
3. A flow battery system for monitoring electrolyte concentration of an all-vanadium flow battery in real time is characterized by comprising:
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 reference detection cavity is provided with a second through hole for the circulation and the updating of a reference solution; the reference solution is an electrolyte with vanadium ions; the second bipolar plate is arranged in the reference detection cavity, a cavity is formed in the part, arranged 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; the aperture of the first through hole is filled with carbon felt or activated carbon; the first through hole is a straight through hole or a bent hole extending and bending along the thickness direction of the insulating plate;
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 empirical formula of the potentials of the positive and negative electrolytes is
Figure FDA0003244529390000041
The potential empirical formula of the cathode electrolyte is
Figure FDA0003244529390000045
In the formula, EIs just、ENegative poleThe potentials of the positive electrolyte and the negative electrolyte are respectively in mV;
Figure FDA0003244529390000046
Figure FDA0003244529390000047
the concentrations of the vanadium ions with valence of 2, 3, 4 and 5 are respectively; a. theIs justThe positive electrode potential empirical formula constant term is 695.4; b isIs justThe potential empirical formula of the positive electrode shows that the coefficient of the 4-valent vanadium ion is-19.1; cIs justThe potential empirical formula of the positive electrode shows that the coefficient of the vanadium ion with the valence of 5 is 165.2; a. theNegative poleThe constant term of the negative electrode potential empirical formula is-746.8; b isNegative poleThe cathode potential empirical formula 2 valence vanadium ion coefficient is-65.9; cNegative poleCathode potential empirical formula 3-valent vanadium ion systemThe number is 129.5;
the concentration monitoring unit is used for determining the concentration of each valence state vanadium ion in the anode electrolyte and the cathode electrolyte to be detected based on the established electrolyte concentration monitoring database, wherein the electrolyte concentration monitoring database comprises an anode electrolyte potential empirical formula, a cathode electrolyte potential empirical formula, a vanadium total substance quantity conservation formula and at least one optional formula in the optional formulas, and the optional formulas comprise a system average valence state formula, an anode vanadium total quantity conservation formula and a cathode vanadium total quantity conservation formula; or the electrolyte concentration monitoring database comprises an anode electrolyte potential empirical formula, a cathode electrolyte potential empirical formula, a vanadium total substance quantity conservation formula, an anode vanadium concentration interval inequality and a cathode vanadium concentration interval inequality;
wherein the quantity conservation formula of the vanadium total substance is
Figure FDA0003244529390000043
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 FDA0003244529390000044
Wherein M is the average valence of vanadium ions in each valence state of the system;
the positive electrode vanadium total conservation formula
Figure FDA0003244529390000051
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 FDA0003244529390000053
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 FDA0003244529390000052
In the formula, cInitial assemblyThe concentration value of the electrolyte initially added into the system;
the negative electrode vanadium concentration interval inequality
Figure FDA0003244529390000054
In the formula, cInitial assemblyIs the concentration value of the electrolyte initially charged into the system.
4. The system for monitoring the electrolyte concentration of the all-vanadium flow battery in real time according to claim 3, wherein: when data sampling is carried out, sampling is carried out 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 and the total vanadium concentration sampling points of the positive electrolyte and the negative electrolyte are not less than 3 in the variation range of the composition of the positive electrolyte and the negative electrolyte of the all-vanadium redox flow energy storage battery system.
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