CN109669142A - A kind of method and system for the migration of real-time monitoring all-vanadium flow battery vanadium - Google Patents
A kind of method and system for the migration of real-time monitoring all-vanadium flow battery vanadium Download PDFInfo
- Publication number
- CN109669142A CN109669142A CN201811140235.5A CN201811140235A CN109669142A CN 109669142 A CN109669142 A CN 109669142A CN 201811140235 A CN201811140235 A CN 201811140235A CN 109669142 A CN109669142 A CN 109669142A
- Authority
- CN
- China
- Prior art keywords
- vanadium
- electrolyte
- negative
- positive
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04537—Electric variables
- H01M8/04544—Voltage
- H01M8/04552—Voltage of the individual fuel cell
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/0444—Concentration; Density
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
- H01M8/04537—Electric variables
- H01M8/04544—Voltage
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04992—Processes for controlling fuel cells or fuel cell systems characterised by the implementation of mathematical or computational algorithms, e.g. feedback control loops, fuzzy logic, neural networks or artificial intelligence
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of method and system for the migration of real-time monitoring all-vanadium flow battery vanadium, comprising: obtain sampled data, it is sampled by positive and negative anodes electrolyte of the SOC detection device to various concentration relative to the potential parameters of reference solution, while anode electrolyte total volume, electrolyte liquid total volume is acquired；Positive/negative electrolyte current potential empirical equation is fitted by sampled data；It establishes concentration of electrolyte monitor database and determines each valence state vanadium ion concentration in positive/negative electrolyte to be measured；Based on each valence state vanadium ion concentration in identified positive/negative electrolyte to be measured, the total vanadium amount of positive/negative is calculated, and then obtain system vanadium the amount of migration；Based on system vanadium the amount of migration calculated, so that positive and negative anodes vanadium amount is restored to initial optimal proportion to the opposite direction adjustment electrolyte of vanadium migration and power system capacity is restored.The present invention convenient can obtain system vanadium the amount of migration, to reach capacity attenuation caused by inhibition is migrated by vanadium.
Description
Technical field
The present invention relates to flow battery technology, it is specifically a kind of for real-time monitoring all-vanadium flow battery vanadium migration
Method and system.
Background technique
Vanadium cell system is with the progress of charge and discharge, and the vanadium ion in electrolyte can be migrated through film, to influence
Power system capacity.
Currently, there are the following problems for solution in the prior art:
1. replacing ionic membrane in pile, using the resistance better film of vanadium effect, but at present, this technology is still immature；
2. periodically the side more than the vanadium adjusts electrolyte to the few side of vanadium, but system is with the difference of operational mode, vanadium
Migratory direction is also different, the amount of migration also different from；And vanadium of the vanadium cell system with the progress of charge and discharge, in electrolyte
Ion can be migrated through film, to influence power system capacity.
In summary, the on-line monitoring method of existing fluid cell electrolyte CONCENTRATION STATE especially offset variation situation
Equal certain drawbacks are not able to satisfy the use demand of real-time monitoring fluid cell electrolyte state.
Summary of the invention
In view of drawback of the existing technology, one aspect of the present invention is provided moves for real-time monitoring all-vanadium flow battery vanadium
The method of shifting, the technical issues of effectively to solve mentioned in background technique.
A method of it is migrated for real-time monitoring all-vanadium flow battery vanadium, which comprises the steps of:
S1, obtain sampled data, i.e., it is molten relative to reference to the positive and negative anodes electrolyte of various concentration by SOC detection device
The potential parameters of liquid are sampled, while being acquired to anode electrolyte total volume, electrolyte liquid total volume；The SOC
Detection device include end plate, the first bipolar plates, positive/negative electrolyte test chamber, amberplex, respectively with the positive/negative
The anode electrolyte the import and export pipeline and electrolyte liquid the import and export pipeline that electrolyte test chamber is connected, it is multiple to offer first
The insulation board of through-hole, reference test chamber and second bipolar plates of the reference test chamber as potential test electrode are placed in,
In, the insulation board is respectively set at the amberplex two sides and is examined with interval reference test chamber and positive/negative electrolyte
Survey chamber；Filled with reference solution in the reference test chamber；
S2, positive/negative electrolyte current potential empirical equation is fitted by sampled data；
Wherein, the anode electrolyte current potential empirical equation is
The electrolyte liquid current potential empirical equation is
In formula, EJust、EIt is negativeRespectively positive and negative electrode electrolyte current potential, unit mV； Respectively
For divalent, trivalent, 4 valences, 5 valence vanadium ion concentrations；AJustFor anodic potentials empirical equation constant term；BJustFor anodic potentials empirical equation 4
Valence vanadium ion coefficient；CJustFor 5 valence vanadium ion coefficient of anodic potentials empirical equation；AIt is negativeFor cathode potential empirical equation constant term；BIt is negative
For cathode potential empirical equation divalent vanadium ion coefficient；CIt is negativeFor cathode potential empirical equation trivalent vanadium ion coefficient；
S3, it establishes concentration of electrolyte monitor database and determines that each valence state vanadium ion is dense in positive/negative electrolyte to be measured
Degree, the concentration of electrolyte monitor database include positive/negative electrolyte current potential empirical equation, vanadium total material amount conservation formula with
And at least one formula or inequality in optional formula/inequality, the optional formula/inequality includes system flat fare
State formula, positive vanadium total amount conservation formula, cathode vanadium total amount conservation formula, positive vanadium concentration ranges inequality and cathode vanadium are dense
Spend section inequality；
S4, based on each valence state vanadium ion concentration in identified positive/negative electrolyte to be measured, it is total to calculate positive/negative
Vanadium amount, and then obtain system vanadium the amount of migration；
S5, it is based on system vanadium the amount of migration calculated, the opposite direction adjustment electrolyte migrated to vanadium keeps positive and negative anodes vanadium amount extensive
Arriving initial optimal proportion again makes power system capacity be restored；
Wherein, vanadium the amount of migration calculation formula is as follows:
In formula, NJust、NIt is negativeThe respectively amount of positive and negative anodes side vanadium ion total material, Respectively
For 2,3,4,5 valence vanadium ion concentrations, VJust、VIt is negativeRespectively anode electrolyte volume, electrolyte liquid product, NMigrationIt is moved for vanadium ion
Shifting amount；
The adjustable strategies of the opposite direction adjustment electrolyte migrated to vanadium are as follows: if NMigrationIt, then need to be from anode to cathode tune for positive value
Whole electrolyte adjusts volume are as follows:
If NMigrationFor negative value, then electrolyte need to be adjusted from cathode to anode, adjust volume are as follows:
Wherein, the vanadium total material amount conservation formula is
V in formulaJust、VIt is negativeRespectively positive and negative electrode electrolyte volume, NAlwaysFor the total material of valence state vanadium ion each in battery system
Amount, unit mol；
The system average valence formula
In formula, M is the average valence of each valence state vanadium ion of system；
The anode vanadium total amount conservation formula
In formula, NJustFor the amount of side of the positive electrode vanadium ion total material, unit mol；
The cathode vanadium total amount conservation formula；
In formula, NIt is negativeFor the amount of negative side vanadium ion total material, unit mol；
The anode vanadium concentration ranges inequality
In formula, cIt is initial totalFor the concentration of electrolyte value being initially added in system；
The cathode vanadium concentration ranges inequality
In formula, cIt is initial totalFor the concentration of electrolyte value being initially added in system.
Further, it when carrying out data sampling, forms and changes in all vanadium flow energy-storage battery system positive and negative anodes electrolyte
In range, 0.2mol/L, positive and negative anodes electrolyte total V density sample point are not more than with different valence state vanadium ion concentration change interval
No less than 3, hydrogen ion concentration sample point is no less than 3 and is sampled for sampling condition.
Further, the test chamber of the SOC detection device is by reference test chamber and anode electrolyte test chamber, cathode
At least one of electrolyte test chamber electrolyte test chamber composition.
Further, the reference test chamber is provided with the second through-hole updated for reference solution circulation.
Further, the reference solution is the electrolyte with vanadium ion.
Further, in the electrolyte vanadium ion valence state range be 3.5 valences valence state or 4 valences and 5 valences mixing
One of valence state.
Further, second bipolar plates, which are placed in inside reference test chamber, is separated by cavity, the aperture face of the cavity
The long-pending proportional region with the reference test chamber chamber internal electrode gross area is 0~1.
Further, the material of second bipolar plates be carbon material, it is metal material, any one in conducting polymer
Kind.
Further, high-specific surface area material or hydrophilic material are filled in the aperture of the first through hole.
Further, the first through hole is clear opening or extends the bending of bending along the insulation plate thickness direction
Hole.
Further, the material of the insulation board is PP insulating materials, PE insulating materials, PVC insulating materials, PVDF insulation
Any one in material, PTFE insulating materials.
Another aspect of the present invention provides a kind of system for capableing of real-time monitoring all-vanadium flow battery side reaction, and feature exists
In, comprising:
Data sampling unit, for molten relative to reference to the positive and negative anodes electrolyte of various concentration by SOC detection device
The potential parameters of liquid are sampled, while being acquired to anode electrolyte total volume, electrolyte liquid total volume；The SOC
Detection device include end plate, the first bipolar plates, positive/negative electrolyte test chamber, amberplex, respectively with the positive/negative
The anode electrolyte the import and export pipeline and electrolyte liquid the import and export pipeline that electrolyte test chamber is connected, it is multiple to offer first
The insulation board of through-hole, reference test chamber and second bipolar plates of the reference test chamber as potential test electrode are placed in,
In, the insulation board is respectively set at the amberplex two sides and is examined with interval reference test chamber and positive/negative electrolyte
Survey chamber；Filled with reference solution in the reference test chamber；
Sampled data fitting unit, for fitting positive/negative electricity by sampled data acquired in data sampling unit
Solve liquid current potential empirical equation；
Wherein, the anode electrolyte current potential empirical equation is
The electrolyte liquid current potential empirical equation is
In formula, EJust、EIt is negativeRespectively positive and negative anodes electrolyte current potential, unit mV； Respectively
Divalent, trivalent, 4 valences, 5 valence vanadium ion concentrations；AJustDetermine each valence state vanadium ion concentration anodic potentials in positive/negative electrolyte to be measured
Empirical equation constant term；BJustFor 4 valence vanadium ion coefficient of anodic potentials empirical equation；CJustFor 5 valence vanadium of anodic potentials empirical equation from
Subsystem number；AIt is negativeFor cathode potential empirical equation constant term；BIt is negativeFor cathode potential empirical equation divalent vanadium ion coefficient；CIt is negativeFor cathode
Current potential empirical equation trivalent vanadium ion coefficient；
Concentration monitor unit, for determining positive/negative electrolysis to be measured based on the concentration of electrolyte monitor database established
Each valence state vanadium ion concentration in liquid, the concentration of electrolyte monitor database include positive/negative electrolyte current potential empirical equation,
Vanadium total material amount conservation formula and at least one formula in optional formula/inequality or inequality determine to be measured positive/negative
Each valence state vanadium ion concentration in the electrolyte of pole, the optional formula/inequality include that system average valence formula, positive vanadium are total
Measure conservation formula, cathode vanadium total amount conservation formula, positive vanadium concentration ranges inequality and cathode vanadium concentration ranges inequality；
System vanadium the amount of migration computing unit, for based on each valence state vanadium in identified positive/negative electrolyte to be measured from
Sub- concentration calculates the total vanadium amount of positive/negative, and then obtains system vanadium the amount of migration；
Capacity restoration unit, for being based on system vanadium the amount of migration calculated, the opposite direction migrated to vanadium adjusts electrolyte
So that positive and negative anodes vanadium amount is restored to initial optimal proportion makes power system capacity be restored.
Wherein, vanadium the amount of migration calculation formula is as follows:
In formula, NJust、NIt is negativeThe respectively amount of positive and negative anodes side vanadium ion total material, Respectively
For 2,3,4,5 valence vanadium ion concentrations, VJust、VIt is negativeRespectively anode electrolyte volume, electrolyte liquid product, NMigrationIt is moved for vanadium ion
Shifting amount；
The adjustable strategies of the opposite direction adjustment electrolyte migrated to vanadium are as follows: if NMigrationIt, then need to be from anode to cathode tune for positive value
Whole electrolyte adjusts volume are as follows:
If NMigrationFor negative value, then electrolyte need to be adjusted from cathode to anode, adjust volume are as follows:
Wherein, the vanadium total material amount conservation formula is
V in formulaJust、VIt is negativeRespectively positive and negative electrode electrolyte volume, NAlwaysFor the total material of valence state vanadium ion each in battery system
Amount, unit mol；
The system average valence formula
In formula, M is the average valence of each valence state vanadium ion of system；
The anode vanadium total amount conservation formula
In formula, NJustFor the amount of side of the positive electrode vanadium ion total material, unit mol；
The cathode vanadium total amount conservation formula；
In formula, NIt is negativeFor the amount of negative side vanadium ion total material, unit mol；
The anode vanadium concentration ranges inequality
In formula, cIt is initial totalFor the concentration of electrolyte value being initially added in system；
The cathode vanadium concentration ranges inequality
In formula, cIt is initial totalFor the concentration of electrolyte value being initially added in system.
Further, it when carrying out data sampling, forms and changes in all vanadium flow energy-storage battery system positive and negative anodes electrolyte
In range, 0.2mol/L, positive and negative anodes electrolyte total V density sample point are not more than with different valence state vanadium ion concentration change interval
No less than 3, hydrogen ion concentration sample point is no less than 3 and is sampled for sampling condition.
Compared with prior art, beneficial effects of the present invention:
The present invention only needs acquisition system positive and negative anodes electrolyte volume and positive and negative anodes electrolyte with respect to the potential difference four of reference liquid
A parameter convenient can obtain system vanadium the amount of migration, reach to reach capacity attenuation caused by inhibition is migrated by vanadium and work as vanadium migration
To influence power system capacity degree when, carry out electrolyte adjustment, so that positive and negative anodes vanadium amount is reached balance, recovery system capacity again.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to do simply to introduce, it should be apparent that, the accompanying drawings in the following description is this hair
Bright some embodiments for those of ordinary skill in the art without any creative labor, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the corresponding SOC structure of the detecting device schematic diagram of the embodiment of the present invention；
Fig. 2 is the first second bipolar plate structure schematic diagram of the corresponding SOC detection device-of the embodiment of the present invention；
Fig. 3 is corresponding-second second bipolar plate structure schematic diagram of SOC detection device of the embodiment of the present invention；
Fig. 4 is the corresponding SOC detection device-panel structure schematic diagram of the embodiment of the present invention；
Fig. 5 is that the corresponding SOC detection device of the embodiment of the present invention-reference solution circulation updates structural schematic diagram；
Fig. 6-Fig. 7 is the corresponding system discharge capacity instance graph of inventive embodiments；
Fig. 8 is the corresponding flow chart of steps of the method for the invention.
In figure: 1, end plate, the 2, first bipolar plates, 3, anode electrolyte test chamber, 4, electrolyte liquid test chamber cavity, 5,
Amberplex, 6, anode electrolyte the import and export pipeline, 7, electrolyte liquid the import and export pipeline, 8, insulation board, 801, first is logical
Hole, 9, reference test chamber, the 10, second bipolar plates, 1001, cavity, the 11, second through-hole, 12, SOC detection device, 13, anode electricity
Solve liquid storage tank, 14, cathode electrolyte storage tank, 15, reference storage tank, 16, valve and pipeline.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
In view of many drawbacks of the existing technology.Such as Fig. 8, the present invention devises a kind of for real-time monitoring all-vanadium flow
The method of battery side reaction, which comprises the steps of: S1, obtain sampled data, that is, pass through SOC detection device pair
The positive and negative anodes electrolyte of various concentration is sampled relative to the potential parameters of reference solution (measures the electrolysis of various concentration positive and negative anodes
Liquid phase for reference liquid current potential when, positive and negative anodes concentration of electrolyte need to consider that 2,3,4,5 valence vanadium ion concentrations and hydrogen ion are dense
Degree), while anode electrolyte total volume, electrolyte liquid total volume are acquired by liquidometer；The SOC detection device
Including end plate, the first bipolar plates, positive/negative electrolyte test chamber, amberplex, respectively with the positive/negative electrolyte examine
The anode electrolyte the import and export pipeline and electrolyte liquid the import and export pipeline that chamber is connected are surveyed, it is multiple to offer the exhausted of first through hole
Listrium, reference test chamber and be placed in second bipolar plates of the reference test chamber as potential test electrode, wherein it is described absolutely
Listrium is respectively set at the amberplex two sides with interval reference test chamber and positive/negative electrolyte test chamber；It is described
Filled with reference solution in reference test chamber；The electrolyte potential parameters include system open loop voltage；
S2, positive/negative electrolyte current potential empirical equation is fitted by sampled data；Wherein, the anode electrolyte electricity
Position empirical equation be
The electrolyte liquid current potential empirical equation is
In formula, EJust、EIt is negativeRespectively positive and negative electrode electrolyte current potential, unit mV； Respectively
For divalent, trivalent, 4 valences, 5 valence vanadium ion concentrations；AJustFor anodic potentials empirical equation constant term；BJustFor anodic potentials empirical equation 4
Valence vanadium ion coefficient；CJustFor 5 valence vanadium ion coefficient of anodic potentials empirical equation；AIt is negativeFor cathode potential empirical equation constant term；BIt is negative
For cathode potential empirical equation divalent vanadium ion coefficient；CIt is negativeFor cathode potential empirical equation trivalent vanadium ion coefficient；
S3, it establishes concentration of electrolyte monitor database and determines that each valence state vanadium ion is dense in positive/negative electrolyte to be measured
Degree, the concentration of electrolyte monitor database include positive/negative electrolyte current potential empirical equation, vanadium total material amount conservation formula with
And at least one formula or inequality in optional formula/inequality, the optional formula/inequality includes system flat fare
State formula, positive vanadium total amount conservation formula, cathode vanadium total amount conservation formula, positive vanadium concentration ranges inequality and cathode vanadium are dense
Spend section inequality；
S4, based on each valence state vanadium ion concentration in identified positive/negative electrolyte to be measured, it is total to calculate positive/negative
Vanadium amount, and then obtain system vanadium the amount of migration；
S5, it is based on system vanadium the amount of migration calculated, the opposite direction adjustment electrolyte migrated to vanadium keeps positive and negative anodes vanadium amount extensive
Arriving initial optimal proportion again makes power system capacity be restored；
Wherein, vanadium the amount of migration calculation formula is as follows:
In formula, NJust、NIt is negativeThe respectively amount of positive and negative anodes side vanadium ion total material, Respectively
For 2,3,4,5 valence vanadium ion concentrations, VJust、VIt is negativeRespectively anode electrolyte volume, electrolyte liquid product, NMigrationIt is moved for vanadium ion
Shifting amount；
The adjustable strategies of the opposite direction adjustment electrolyte migrated to vanadium are as follows: if NMigrationIt, then need to be from anode to cathode tune for positive value
Whole electrolyte adjusts volume are as follows:
If NMigrationFor negative value, then electrolyte need to be adjusted from cathode to anode, adjust volume are as follows:
Wherein, the vanadium total material amount conservation formula is
V in formulaJust、VIt is negativeRespectively positive and negative electrode electrolyte volume, NAlwaysFor the total material of valence state vanadium ion each in battery system
Amount, unit mol；
The system average valence formula
In formula, M is the average valence of each valence state vanadium ion of system；
The anode vanadium total amount conservation formula
In formula, NJustFor the amount of side of the positive electrode vanadium ion total material, unit mol；
The cathode vanadium total amount conservation formula；
In formula, NIt is negativeFor the amount of negative side vanadium ion total material, unit mol；
The anode vanadium concentration ranges inequality
In formula, cIt is initial totalFor the concentration of electrolyte value being initially added in system；
The cathode vanadium concentration ranges inequality
In formula, cIt is initial totalFor the concentration of electrolyte value being initially added in system.
In a kind of optional embodiment, when carrying out data sampling, in all vanadium flow energy-storage battery system positive and negative anodes
Electrolyte forms in variation range, is not more than 0.2mol/L, positive and negative anodes electrolyte with different valence state vanadium ion concentration change interval
Total V density sample point is no less than 3, and hydrogen ion concentration sample point is no less than 3 and is sampled for sampling condition.
In a kind of optional embodiment, the test chamber of the SOC detection device is by with following several combining forms:
It is made of two kinds of test chambers of reference test chamber and anode electrolyte test chamber；Or by reference test chamber and electrolyte liquid
Two kinds of test chamber compositions of test chamber；Or by reference test chamber, anode electrolyte test chamber, electrolyte liquid test chamber and 3
Kind electrolyte test chamber composition.
In a kind of optional embodiment, the reference test chamber is provided with second updated for reference solution circulation and leads to
Hole.
In a kind of optional embodiment, the reference solution is the electrolyte with vanadium ion.Preferably, the electricity
The valence state range of vanadium ion in liquid is solved as any one valence state model in the mixed valence of the valence state of 3.5 valences or 4 valences and 5 valences
It encloses.
In a kind of optional embodiment, the part that second bipolar plates are placed in reference test chamber is provided with cavity,
The shape of the cavity is unlimited, but the proportional region of its perforated area and the reference test chamber chamber internal electrode gross area is 0~1.
In a kind of optional embodiment, the material of second bipolar plates is carbon material, metal material, conducting polymer
Any one in object.
In a kind of optional embodiment, since the first through hole needs to fill solution, the hole of first through hole
High-specific surface area material or hydrophilic material are filled in diameter, it is preferred to use the materials such as carbon felt, active carbon.
In a kind of optional embodiment, the first through hole is clear opening or prolongs along the insulation plate thickness direction
The bending hole of bending is stretched to form capillary structure and make reference test chamber and positive reference test chamber and reference test chamber and bear
Pole reference test chamber passes through the capillary structure and is connected.
In a kind of optional embodiment, the material of the insulation board is PP insulating materials, PE insulating materials, PVC exhausted
Edge material, PVDF insulating materials, any one in PTFE insulating materials.
Another aspect of the present invention provides the flow battery system based on the SOC detection device.
Another aspect of the present invention provides a kind of system for capableing of real-time monitoring all-vanadium flow battery side reaction, and feature exists
In, comprising:
Data sampling unit, for molten relative to reference to the positive and negative anodes electrolyte of various concentration by SOC detection device
The potential parameters of liquid are sampled, while being acquired to anode electrolyte total volume, electrolyte liquid total volume；The SOC
Detection device include end plate, the first bipolar plates, positive/negative electrolyte test chamber, amberplex, respectively with the positive/negative
The anode electrolyte the import and export pipeline and electrolyte liquid the import and export pipeline that electrolyte test chamber is connected, it is multiple to offer first
The insulation board of through-hole, reference test chamber and second bipolar plates of the reference test chamber as potential test electrode are placed in,
In, the insulation board is respectively set at the amberplex two sides and is examined with interval reference test chamber and positive/negative electrolyte
Survey chamber；Filled with reference solution in the reference test chamber；
Sampled data fitting unit, for fitting positive/negative electricity by sampled data acquired in data sampling unit
Solve liquid current potential empirical equation；
Wherein, the anode electrolyte current potential empirical equation is
The electrolyte liquid current potential empirical equation is
In formula, EJust、EIt is negativeRespectively positive and negative electrode electrolyte current potential, unit mV； Respectively
For divalent, trivalent, 4 valences, 5 valence vanadium ion concentrations；AJustFor anodic potentials empirical equation constant term；BJustFor anodic potentials empirical equation 4
Valence vanadium ion coefficient；CJustFor 5 valence vanadium ion coefficient of anodic potentials empirical equation；AIt is negativeFor cathode potential empirical equation constant term；BIt is negative
For cathode potential empirical equation divalent vanadium ion coefficient；CIt is negativeFor cathode potential empirical equation trivalent vanadium ion coefficient；
Concentration monitor unit, for determining positive/negative electrolysis to be measured based on the concentration of electrolyte monitor database established
Each valence state vanadium ion concentration in liquid, the concentration of electrolyte monitor database include positive/negative electrolyte current potential empirical equation,
Vanadium total material amount conservation formula and at least one formula in optional formula/inequality or inequality determine to be measured positive/negative
Each valence state vanadium ion concentration in the electrolyte of pole, the optional formula/inequality include that system average valence formula, positive vanadium are total
Measure conservation formula, cathode vanadium total amount conservation formula, positive vanadium concentration ranges inequality and cathode vanadium concentration ranges inequality；
Wherein, the vanadium total material amount conservation formula is
V in formulaJust、VIt is negativeRespectively positive and negative electrode electrolyte volume, NAlwaysFor the total material of valence state vanadium ion each in battery system
Amount, unit mol；
The system average valence formula
In formula, M is the average valence of each valence state vanadium ion of system；
The anode vanadium total amount conservation formula
In formula, NJustFor the amount of side of the positive electrode vanadium ion total material, unit mol；
The cathode vanadium total amount conservation formula；
In formula, NIt is negativeFor the amount of negative side vanadium ion total material, unit mol；
The anode vanadium concentration ranges inequality
In formula, cIt is initial totalFor the concentration of electrolyte value being initially added in system；
The cathode vanadium concentration ranges inequality
In formula, cIt is initial totalFor the concentration of electrolyte value being initially added in system；
System vanadium the amount of migration computing unit, for based on each valence state vanadium in identified positive/negative electrolyte to be measured from
Sub- concentration calculates the total vanadium amount of positive/negative, and then obtains system vanadium the amount of migration；
Capacity restoration unit, for being based on system vanadium the amount of migration calculated, the opposite direction migrated to vanadium adjusts electrolyte
So that positive and negative anodes vanadium amount is restored to initial optimal proportion makes power system capacity be restored.
Wherein, vanadium the amount of migration calculation formula is as follows:
In formula, NJust、NIt is negativeThe respectively amount of positive and negative anodes side vanadium ion total material, Respectively
For 2,3,4,5 valence vanadium ion concentrations, VJust、VIt is negativeRespectively anode electrolyte volume, electrolyte liquid product, NMigrationIt is moved for vanadium ion
Shifting amount；
The adjustable strategies of the opposite direction adjustment electrolyte migrated to vanadium are as follows: if NMigrationIt, then need to be from anode to cathode tune for positive value
Whole electrolyte adjusts volume are as follows:
If NMigrationFor negative value, then electrolyte need to be adjusted from cathode to anode, adjust volume are as follows:
Further, it when carrying out data sampling, forms and changes in all vanadium flow energy-storage battery system positive and negative anodes electrolyte
In range, 0.2mol/L, positive and negative anodes electrolyte total V density sample point are not more than with different valence state vanadium ion concentration change interval
No less than 3, hydrogen ion concentration sample point is no less than 3 and is sampled for sampling condition.
Based on above-mentioned design scheme, it is further described and proves by taking embodiment as Figure 1-Figure 5 as an example, the example
Use the test chamber of the SOC detection device 12 by reference test chamber, anode electrolyte test chamber, electrolyte liquid test chamber with
And 3 kinds of electrolyte test chamber compositions；Specifically, a kind of SOC detection of detection flow battery electrolyte inside state as shown in Figure 1
Device comprising end plate 1, the first bipolar plates 2, anode electrolyte test chamber 3, electrolyte liquid test chamber 4, amberplex 5,
The anode electrolyte the import and export pipeline 6 being connected respectively with the positive/negative electrolyte test chamber (connect anolyte liquid storage tank
13) with electrolyte liquid the import and export pipeline 7 (connecting cathode electrolyte storage tank 14)；4 offer the insulation board of first through hole 801
8, it is provided with the reference test chamber 9 of the second through-hole 11 updated for reference solution circulation and is placed in the reference test chamber as electricity
Second bipolar plates 10 of bit test electrode, the insulation board 9 are respectively set at 5 two sides of amberplex with interval reference
Test chamber 9 is with positive/negative electrolyte test chamber (i.e. so that anode electrolyte test chamber and/or electrolyte liquid test chamber pass through
Ionic membrane and insulation board and reference chamber separate)；Filled with reference solution in the reference test chamber.
Wherein, the reference solution is the electrolyte with vanadium ion, and the valence state range of the vanadium ion is 4 valences and 5 valences
Mixed valence in；The part that second bipolar plates are placed in reference test chamber is provided with square cavity 1001 as shown in Figure 2,
It can also structure as shown in Figure 3；The material of second bipolar plates is carbon material；Carbon felt is filled in the aperture of the first through hole
Material；As shown in figure 4, the first through hole is capillary structure (the longer the better for the length of aperture)；The material of the insulation board
For PVC insulating materials；As shown in figure 5, the reference test chamber is provided with the second through-hole updated for reference solution circulation, pass through valve
Door is sent reference solution by the second through-hole to reference test chamber from reference storage tank 15 with pipeline 16；
Wherein positive/negative electrolyte current potential empirical equation；
Wherein, the anode electrolyte current potential empirical equation is
The electrolyte liquid current potential empirical equation is
In formula, EJust、EIt is negativeRespectively positive and negative anodes electrolyte current potential, unit mV； Respectively
Divalent, trivalent, 4 valences, 5 valence vanadium ion concentrations；AJustAnodic potentials empirical equation constant term, preferred value 695.4；BJustAnodic potentials warp
4 valence vanadium ion coefficient of formula is tested, preferred value is -19.1；CJust5 valence vanadium ion coefficient of anodic potentials empirical equation, preferred value are
165.2；AIt is negativeCathode potential empirical equation constant term, preferred value are -746.8；BIt is negativeCathode potential empirical equation divalent vanadium ion system
Number, preferred value are -65.9；CIt is negativeCathode potential empirical equation trivalent vanadium ion coefficient, preferred value 129.5；
Finally choose comprising above-mentioned formula 1., 2., 3. and optionally 4. -8. including no less than four equations or inequality
Simultaneous, solving equations obtain each valence state vanadium ion concentration in positive and negative anodes electrolyte；
S4, based on each valence state vanadium ion concentration in identified positive/negative electrolyte to be measured, it is total to calculate positive/negative
Vanadium amount, and then obtain system vanadium the amount of migration；
S5, it is based on system vanadium the amount of migration calculated, the opposite direction adjustment electrolyte migrated to vanadium keeps positive and negative anodes vanadium amount extensive
Arriving initial optimal proportion again makes power system capacity be restored.
Wherein, vanadium the amount of migration calculation formula is as follows:
In formula, NJust、NIt is negativeThe respectively amount of positive and negative anodes side vanadium ion total material, Respectively
For 2,3,4,5 valence vanadium ion concentrations, VJust、VIt is negativeRespectively anode electrolyte volume, electrolyte liquid product, NMigrationIt is moved for vanadium ion
Shifting amount；
The adjustable strategies of the opposite direction adjustment electrolyte migrated to vanadium are as follows: if NMigrationIt, then need to be from anode to cathode tune for positive value
Whole electrolyte adjusts volume are as follows:
If NMigrationFor negative value, then electrolyte need to be adjusted from cathode to anode, adjust volume are as follows:
Specific calculated examples are referring to embodiment 1,2:
Embodiment 1
Current potential, volume and the calculated vanadium concentration of 1 2kW service system of table monitoring
The total vanadium amount N of positive and negative anodesJust=37.4*1.605=60.027mol, NIt is negativeThe total vanadium of=42.6*1.560=66.456mol to
Cathode migration, if wanting, electrolyte volume need to be adjusted to anode by reaching the equal state of the total vanadium amount of the initial positive and negative anodes of system
Electrolyte adjusts back positive front and back system discharge capacity such as Fig. 6 by cathode, it can be seen that is adjusted, power system capacity
Restored.
Embodiment 2
Current potential, volume and the calculated vanadium concentration of 1 2kW service system of table monitoring
The total vanadium amount N of positive and negative anodesJust=43.2*1.605=69.336mol, NIt is negativeThe total vanadium of=36.8*1.604=59.027mol to
Anode migration, if wanting, electrolyte volume need to be adjusted to cathode by reaching the equal state of the total vanadium amount of the initial positive and negative anodes of system
Electrolyte adjusts back cathode front and back system discharge capacity such as Fig. 7 by anode, it can be seen that is adjusted, power system capacity
Restored.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of method for the migration of real-time monitoring all-vanadium flow battery vanadium, which comprises the steps of:
S1, sampled data is obtained, that is, passes through SOC detection device to the positive and negative anodes electrolyte of various concentration relative to reference solution
Potential parameters are sampled, while being acquired to anode electrolyte total volume, electrolyte liquid total volume；The SOC detection
Device include end plate, the first bipolar plates, positive/negative electrolyte test chamber, amberplex, respectively with the positive/negative be electrolysed
The anode electrolyte the import and export pipeline and electrolyte liquid the import and export pipeline that liquid test chamber is connected, it is multiple to offer first through hole
Insulation board, reference test chamber and be placed in second bipolar plates of the reference test chamber as potential test electrode, wherein institute
It states insulation board and is respectively set at the amberplex two sides with interval reference test chamber and positive/negative electrolyte test chamber；
Filled with reference solution in the reference test chamber；
S2, positive/negative electrolyte current potential empirical equation is fitted by sampled data；
Wherein, the anode electrolyte current potential empirical equation is
The electrolyte liquid current potential empirical equation is
In formula, EJust、EIt is negativeRespectively positive and negative electrode electrolyte current potential, unit mV； Respectively 2
Valence, trivalent, 4 valences, 5 valence vanadium ion concentrations；AJustFor anodic potentials empirical equation constant term；BJustFor 4 valence vanadium of anodic potentials empirical equation
Ion coefficient；CJustFor 5 valence vanadium ion coefficient of anodic potentials empirical equation；AIt is negativeFor cathode potential empirical equation constant term；BIt is negativeIt is negative
Electrode potential empirical equation divalent vanadium ion coefficient；CIt is negativeFor cathode potential empirical equation trivalent vanadium ion coefficient；
S3, it establishes concentration of electrolyte monitor database and determines each valence state vanadium ion concentration in positive/negative electrolyte to be measured, institute
Stating concentration of electrolyte monitor database includes positive/negative electrolyte current potential empirical equation, vanadium total material amount conservation formula and can
At least one formula or the inequality in formula/inequality are selected, the optional formula/inequality includes that system average valence is public
Formula, positive vanadium total amount conservation formula, cathode vanadium total amount conservation formula, positive vanadium concentration ranges inequality and cathode vanadium concentration area
Between inequality；
S4, based on each valence state vanadium ion concentration in identified positive/negative electrolyte to be measured, calculate the total vanadium amount of positive/negative,
And then obtain system vanadium the amount of migration；
S5, it is based on system vanadium the amount of migration calculated, the opposite direction adjustment electrolyte migrated to vanadium is restored to positive and negative anodes vanadium amount
Initial optimal proportion makes power system capacity be restored.
2. the method according to claim 1 for the migration of real-time monitoring all-vanadium flow battery vanadium, it is characterised in that:
Wherein, vanadium the amount of migration calculation formula is as follows:
In formula, NJust、NIt is negativeThe respectively amount of positive and negative anodes side vanadium ion total material, Respectively 2,
3,4,5 valence vanadium ion concentration, VJust、VIt is negativeRespectively anode electrolyte volume, electrolyte liquid product, NMigrationFor vanadium ion the amount of migration；
The adjustable strategies of the opposite direction adjustment electrolyte migrated to vanadium are as follows: if NMigrationFor positive value, then electricity need to be adjusted from anode to cathode
Liquid is solved, volume is adjusted are as follows:
If NMigrationFor negative value, then electrolyte need to be adjusted from cathode to anode, adjust volume are as follows:
Wherein, the vanadium total material amount conservation formula is
V in formulaJust、VIt is negativeRespectively positive and negative electrode electrolyte volume, NAlwaysFor the amount of the total material of valence state vanadium ion each in battery system,
Unit is mol；
The system average valence formula
In formula, M is the average valence of each valence state vanadium ion of system；
The anode vanadium total amount conservation formula
In formula, NJustFor the amount of side of the positive electrode vanadium ion total material, unit mol；
The cathode vanadium total amount conservation formula；
In formula, NIt is negativeFor the amount of negative side vanadium ion total material, unit mol；
The anode vanadium concentration ranges inequality
In formula, cIt is initial totalFor the concentration of electrolyte value being initially added in system；
The cathode vanadium concentration ranges inequality
In formula, cIt is initial totalFor the concentration of electrolyte value being initially added in system.
3. the method according to claim 1 or 2 for the side reaction of real-time monitoring all-vanadium flow battery, feature exist
In:
When carrying out data sampling, in all vanadium flow energy-storage battery system positive and negative anodes electrolyte composition variation range, with difference
Valence state vanadium ion concentration change interval is not more than 0.2mol/L, and positive and negative anodes electrolyte total V density sample point is no less than 3, hydrogen from
Sub- concentration sample point is no less than 3 and is sampled for sampling condition.
4. the method according to claim 1 for the side reaction of real-time monitoring all-vanadium flow battery, it is characterised in that:
The test chamber of the SOC detection device is by reference test chamber and anode electrolyte test chamber, electrolyte liquid test chamber
At least one of electrolyte test chamber composition.
5. the method according to claim 1 for the side reaction of real-time monitoring all-vanadium flow battery, it is characterised in that:
The reference test chamber is provided with the second through-hole updated for reference solution circulation.
6. the method according to claim 1 for the side reaction of real-time monitoring all-vanadium flow battery, it is characterised in that:
The reference solution is the electrolyte with vanadium ion.
7. the method according to claim 1 for the side reaction of real-time monitoring all-vanadium flow battery, it is characterised in that:
Second bipolar plates, which are placed in inside reference test chamber, is separated by cavity, the perforated area and reference test chamber of the cavity
The proportional region of the chamber internal electrode gross area is 0~1.
8. the method according to claim 1 for the side reaction of real-time monitoring all-vanadium flow battery, it is characterised in that:
The first through hole is clear opening or extends the bending hole of bending along the insulation plate thickness direction.
9. the system that one kind is capable of the migration of real-time monitoring all-vanadium flow battery vanadium characterized by comprising
Data sampling unit, for passing through SOC detection device to the positive and negative anodes electrolyte of various concentration relative to reference solution
Potential parameters are sampled, while being acquired to anode electrolyte total volume, electrolyte liquid total volume；The SOC detection
Device include end plate, the first bipolar plates, positive/negative electrolyte test chamber, amberplex, respectively with the positive/negative be electrolysed
The anode electrolyte the import and export pipeline and electrolyte liquid the import and export pipeline that liquid test chamber is connected, it is multiple to offer first through hole
Insulation board, reference test chamber and be placed in second bipolar plates of the reference test chamber as potential test electrode, wherein institute
It states insulation board and is respectively set at the amberplex two sides with interval reference test chamber and positive/negative electrolyte test chamber；
Filled with reference solution in the reference test chamber；
Sampled data fitting unit, for fitting positive/negative electrolyte by sampled data acquired in data sampling unit
Current potential empirical equation；
Wherein, the anode electrolyte current potential empirical equation is
The electrolyte liquid current potential empirical equation is
In formula, EJust、EIt is negativeRespectively positive and negative anodes electrolyte current potential, unit mV； Respectively divalent,
Trivalent, 4 valences, 5 valence vanadium ion concentrations；AJustFor anodic potentials empirical equation constant term；BJustFor 4 valence vanadium of anodic potentials empirical equation from
Subsystem number；CJustFor 5 valence vanadium ion coefficient of anodic potentials empirical equation；AIt is negativeFor cathode potential empirical equation constant term；BIt is negativeFor cathode
Current potential empirical equation divalent vanadium ion coefficient；CIt is negativeFor cathode potential empirical equation trivalent vanadium ion coefficient；
Concentration monitor unit, for being determined based on the concentration of electrolyte monitor database established in positive/negative electrolyte to be measured
Each valence state vanadium ion concentration, the concentration of electrolyte monitor database include that positive/negative electrolyte current potential empirical equation, vanadium are total
Amount of substance conservation formula and at least one formula in optional formula/inequality or inequality determine positive/negative electricity to be measured
Solve each valence state vanadium ion concentration in liquid, the optional formula/inequality includes that system average valence formula, positive vanadium total amount are kept
Permanent formula, cathode vanadium total amount conservation formula, positive vanadium concentration ranges inequality and cathode vanadium concentration ranges inequality；
System vanadium the amount of migration computing unit, for dense based on each valence state vanadium ion in identified positive/negative electrolyte to be measured
Degree, calculates the total vanadium amount of positive/negative, and then obtain system vanadium the amount of migration；
Capacity restoration unit, for being based on system vanadium the amount of migration calculated, the opposite direction adjustment electrolyte migrated to vanadium makes just
Cathode vanadium amount is restored to initial optimal proportion and power system capacity is restored.
10. the system according to claim 9 for the migration of real-time monitoring all-vanadium flow battery vanadium, it is characterised in that:
Wherein, vanadium the amount of migration calculation formula is as follows:
In formula, NJust、NIt is negativeThe respectively amount of positive and negative anodes side vanadium ion total material, Respectively 2,
3,4,5 valence vanadium ion concentration, VJust、VIt is negativeRespectively anode electrolyte volume, electrolyte liquid product, NMigrationFor vanadium ion the amount of migration；
The adjustable strategies of the opposite direction adjustment electrolyte migrated to vanadium are as follows: if NMigrationFor positive value, then electricity need to be adjusted from anode to cathode
Liquid is solved, volume is adjusted are as follows:
If NMigrationFor negative value, then electrolyte need to be adjusted from cathode to anode, adjust volume are as follows:
Wherein, the vanadium total material amount conservation formula is
V in formulaJust、VIt is negativeRespectively positive and negative electrode electrolyte volume, NAlwaysFor the amount of the total material of valence state vanadium ion each in battery system,
Unit is mol；
The system average valence formula
In formula, M is the average valence of each valence state vanadium ion of system；
The anode vanadium total amount conservation formula
In formula, NJustFor the amount of side of the positive electrode vanadium ion total material, unit mol；
The cathode vanadium total amount conservation formula；
In formula, NIt is negativeFor the amount of negative side vanadium ion total material, unit mol；
The anode vanadium concentration ranges inequality
In formula, cIt is initial totalFor the concentration of electrolyte value being initially added in system；
The cathode vanadium concentration ranges inequality
In formula, cIt is initial totalFor the concentration of electrolyte value being initially added in system.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710893217 | 2017-09-28 | ||
| CN2017108932173 | 2017-09-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109669142A true CN109669142A (en) | 2019-04-23 |
| CN109669142B CN109669142B (en) | 2021-12-31 |
Family
ID=65664701
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811140231.7A Active CN109546186B (en) | 2017-09-28 | 2018-09-28 | SOC detection device and method for detecting state of electrolyte in flow battery and flow battery system with SOC detection device |
| CN201811140235.5A Active CN109669142B (en) | 2017-09-28 | 2018-09-28 | Method and system for monitoring vanadium migration of all-vanadium redox flow battery in real time |
| CN201811140234.0A Active CN109494388B (en) | 2017-09-28 | 2018-09-28 | Method and system for monitoring side reaction of all-vanadium redox flow battery in real time |
| CN201811140260.3A Active CN109473703B (en) | 2017-09-28 | 2018-09-28 | Method and system for monitoring electrolyte concentration of all-vanadium redox flow battery in real time |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811140231.7A Active CN109546186B (en) | 2017-09-28 | 2018-09-28 | SOC detection device and method for detecting state of electrolyte in flow battery and flow battery system with SOC detection device |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811140234.0A Active CN109494388B (en) | 2017-09-28 | 2018-09-28 | Method and system for monitoring side reaction of all-vanadium redox flow battery in real time |
| CN201811140260.3A Active CN109473703B (en) | 2017-09-28 | 2018-09-28 | Method and system for monitoring electrolyte concentration of all-vanadium redox flow battery in real time |
Country Status (1)
| Country | Link |
|---|---|
| CN (4) | CN109546186B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110534775A (en) * | 2019-09-03 | 2019-12-03 | 中国科学院金属研究所 | A kind of flow battery positive and negative anodes electrolyte migration control method |
| CN111551610A (en) * | 2020-04-07 | 2020-08-18 | 上海电气集团股份有限公司 | Vanadium electrolyte concentration testing method, miniature vanadium battery and vanadium electrolyte concentration testing device |
| CN114636747A (en) * | 2022-05-10 | 2022-06-17 | 上海柏中观澈智能科技有限公司 | Substance detection device and method and liquid quality monitoring equipment |
| CN114899460A (en) * | 2022-05-24 | 2022-08-12 | 寰泰储能科技股份有限公司 | Electrolyte vanadium concentration regulation and control method and device of all-vanadium liquid flow energy storage system |
| CN117393810A (en) * | 2023-12-12 | 2024-01-12 | 江苏美淼储能科技有限公司 | Method for recovering capacity of vanadium battery on line and inhibiting diffusion of vanadium ion across membrane on line |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111198218B (en) * | 2020-02-27 | 2021-04-16 | 浙江大学 | Method and device for measuring electrical characteristics of high-temperature oil-based drilling fluid |
| CN111509278B (en) * | 2020-03-20 | 2023-03-17 | 香港科技大学 | Method for recovering capacity and efficiency of all-vanadium redox flow battery on line |
| CN112415077B (en) * | 2020-11-19 | 2022-06-10 | 湖南钒谷新能源技术有限公司 | Method for detecting electrolyte of all-vanadium redox flow battery |
| CN112864427B (en) * | 2020-12-31 | 2024-04-02 | 大连融科储能装备有限公司 | On-line monitoring device and method based on state of charge of flow battery |
| CN112928313B (en) * | 2021-01-28 | 2022-04-22 | 湖南钒谷新能源技术有限公司 | Electrolyte linkage adjusting method and system for vanadium battery system |
| CN113131020B (en) * | 2021-05-08 | 2022-02-22 | 深圳市驰普科达科技有限公司 | Big health management system of industrial battery pack |
| CN113437334B (en) * | 2021-06-22 | 2022-07-05 | 中国科学院上海高等研究院 | Vanadium ion concentration monitoring method, vanadium battery SOC monitoring method, equipment and medium |
| CN115064740A (en) * | 2022-06-20 | 2022-09-16 | 大连融科储能装备有限公司 | Method for monitoring chargeable and dischargeable quantity in real time for all-vanadium liquid flow energy storage system |
| CN115655383B (en) * | 2022-12-27 | 2023-04-07 | 杭州德海艾科能源科技有限公司 | Method and system for detecting valence state imbalance state of electrolyte of all-vanadium redox flow battery |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000012064A (en) * | 1998-06-25 | 2000-01-14 | Sumitomo Electric Ind Ltd | Vanadium redox battery electrolyte and vanadium redox battery using the same |
| JP2004071165A (en) * | 2002-08-01 | 2004-03-04 | Nippon Oil Corp | Production method for electrolyte for vanadium redox battery |
| CN101609128A (en) * | 2009-07-22 | 2009-12-23 | 北京普能世纪科技有限公司 | A kind of method and device of testing the comprehensive valence state of electrolyte of vanadium redox battery |
| CN101614794A (en) * | 2009-07-14 | 2009-12-30 | 清华大学 | A kind of method for online detecting charge state of flow battery based on potential difference parameter |
| CN101619465A (en) * | 2008-07-02 | 2010-01-06 | 中国科学院大连化学物理研究所 | Method for preparing vanadium battery solution or adjusting capacity and special device thereof |
| CN102279218A (en) * | 2011-03-04 | 2011-12-14 | 国网电力科学研究院武汉南瑞有限责任公司 | Method for monitoring vanadium ion concentration of all-vanadium redox flow battery on line |
| CN102299362A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Vanadium redox energy storage battery system and electrolyte flow stepped control strategy thereof |
| CN102341946A (en) * | 2010-03-12 | 2012-02-01 | 住友电气工业株式会社 | Redox flow battery |
| CN103367785A (en) * | 2013-07-17 | 2013-10-23 | 大连融科储能技术发展有限公司 | All-vanadium redox flow battery and operation method thereof |
| CN103762377A (en) * | 2014-01-27 | 2014-04-30 | 中国东方电气集团有限公司 | Vanadium redox battery and electrolyte rebalancing method thereof |
| CN104181158A (en) * | 2014-08-22 | 2014-12-03 | 武钢集团昆明钢铁股份有限公司 | Method for measuring concentration of tetravalent and pentavalent vanadium ions in vanadium battery electrolyte |
| CN104614678A (en) * | 2015-01-21 | 2015-05-13 | 哈尔滨工业大学 | Online detection device and method of battery electrode level in lead-acid storage battery inner chemosynthesis process |
| CN104638288A (en) * | 2013-11-06 | 2015-05-20 | 中国人民解放军63971部队 | Electrochemical preparation method of 3.5 valence vanadium electrolyte |
| US20150303504A1 (en) * | 2014-04-21 | 2015-10-22 | Unienergy Technologies, Llc | Methods for determining and/or adjusting redox-active element concentrations in redox flow batteries |
| CN105144455A (en) * | 2013-05-03 | 2015-12-09 | 联合工艺公司 | Method of maintaining health of a flow battery |
| CN105388127A (en) * | 2015-10-30 | 2016-03-09 | 清华大学深圳研究生院 | Online detecting method and system for concentration of all ions of all-vanadium redox flow battery |
| CN105702997A (en) * | 2016-04-11 | 2016-06-22 | 苏州久润能源科技有限公司 | Redox flow battery rebalance system, refox flow battery system and method for cycle capacity rebalance of redox flow battery |
| EP3077791A1 (en) * | 2013-12-02 | 2016-10-12 | University of Limerick | Method for determining the state of charge of a vanadium redox flow battery |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0059208A1 (en) * | 1980-09-05 | 1982-09-08 | Energy Innovations Inc. | Voltage generating device utilizing thermovoltaic cells and method of making |
| CN102246385B (en) * | 2008-10-10 | 2015-07-29 | 艾默吉电力系统股份有限公司 | For determining the method and apparatus of the state-of-charge of battery |
| CN101839964B (en) * | 2010-05-11 | 2012-07-04 | 三一电气有限责任公司 | Method and device for measuring charge state of all-vanadium redox flow battery in real time |
| JP5772366B2 (en) * | 2011-08-05 | 2015-09-02 | 住友電気工業株式会社 | Redox flow battery |
| CN102621085B (en) * | 2012-03-22 | 2013-11-06 | 湖南农业大学 | Method for online detection of concentration of electrolyte of vanadium battery |
| WO2016025644A1 (en) * | 2014-08-12 | 2016-02-18 | Unienergy Technologies, Llc | Electrochemical cell having a plurality of electrolyte flow areas |
| CN104300165B (en) * | 2014-11-03 | 2016-09-07 | 大连融科储能技术发展有限公司 | A kind of SOC detection devices and methods therefor and flow battery system |
| CN104865226B (en) * | 2015-06-24 | 2017-07-14 | 清华大学深圳研究生院 | A kind of method for quick and device of the side reaction of all-vanadium flow battery positive pole |
| WO2017035257A1 (en) * | 2015-08-24 | 2017-03-02 | The Regents Of The University Of California | All-iron redox flow battery tailored for off-grid portable applications |
| CN106532079B (en) * | 2015-09-08 | 2019-02-01 | 中国科学院大连化学物理研究所 | A kind of recycling and reusing method of vanadium redox flow battery electrolyte |
| CN105355946B (en) * | 2015-10-12 | 2018-03-23 | 华北电力科学研究院有限责任公司 | The in-situ monitoring method and system of vanadium cell both positive and negative polarity electrolyte state-of-charge |
| CN106654421B (en) * | 2015-11-03 | 2019-08-27 | 大连融科储能技术发展有限公司 | Flow battery actual capacity determines method and device thereof |
| CN105425164B (en) * | 2015-12-25 | 2018-05-04 | 华北电力科学研究院有限责任公司 | Charge state of all-vanadium redox flow battery on-line monitoring method and system |
| CN105467328B (en) * | 2015-12-29 | 2018-07-03 | 哈尔滨工业大学 | A kind of charge states of lithium ion battery method of estimation |
| CN105807230B (en) * | 2016-03-11 | 2019-03-26 | 郑贵林 | Remaining battery capacity and health status rapid detection method and device |
| CN107204480B (en) * | 2016-03-14 | 2020-04-24 | 大连融科储能技术发展有限公司 | Method and system for determining electrolyte parameters of flow battery and flow battery |
| CN106450371B (en) * | 2016-11-11 | 2019-02-15 | 攀钢集团攀枝花钢铁研究院有限公司 | A method of recycling failure V electrolyte |
-
2018
- 2018-09-28 CN CN201811140231.7A patent/CN109546186B/en active Active
- 2018-09-28 CN CN201811140235.5A patent/CN109669142B/en active Active
- 2018-09-28 CN CN201811140234.0A patent/CN109494388B/en active Active
- 2018-09-28 CN CN201811140260.3A patent/CN109473703B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000012064A (en) * | 1998-06-25 | 2000-01-14 | Sumitomo Electric Ind Ltd | Vanadium redox battery electrolyte and vanadium redox battery using the same |
| JP2004071165A (en) * | 2002-08-01 | 2004-03-04 | Nippon Oil Corp | Production method for electrolyte for vanadium redox battery |
| CN101619465A (en) * | 2008-07-02 | 2010-01-06 | 中国科学院大连化学物理研究所 | Method for preparing vanadium battery solution or adjusting capacity and special device thereof |
| CN101614794A (en) * | 2009-07-14 | 2009-12-30 | 清华大学 | A kind of method for online detecting charge state of flow battery based on potential difference parameter |
| CN101609128A (en) * | 2009-07-22 | 2009-12-23 | 北京普能世纪科技有限公司 | A kind of method and device of testing the comprehensive valence state of electrolyte of vanadium redox battery |
| CN102341946A (en) * | 2010-03-12 | 2012-02-01 | 住友电气工业株式会社 | Redox flow battery |
| CN102299362A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Vanadium redox energy storage battery system and electrolyte flow stepped control strategy thereof |
| CN102279218A (en) * | 2011-03-04 | 2011-12-14 | 国网电力科学研究院武汉南瑞有限责任公司 | Method for monitoring vanadium ion concentration of all-vanadium redox flow battery on line |
| CN105144455A (en) * | 2013-05-03 | 2015-12-09 | 联合工艺公司 | Method of maintaining health of a flow battery |
| CN103367785A (en) * | 2013-07-17 | 2013-10-23 | 大连融科储能技术发展有限公司 | All-vanadium redox flow battery and operation method thereof |
| CN104638288A (en) * | 2013-11-06 | 2015-05-20 | 中国人民解放军63971部队 | Electrochemical preparation method of 3.5 valence vanadium electrolyte |
| EP3077791A1 (en) * | 2013-12-02 | 2016-10-12 | University of Limerick | Method for determining the state of charge of a vanadium redox flow battery |
| CN103762377A (en) * | 2014-01-27 | 2014-04-30 | 中国东方电气集团有限公司 | Vanadium redox battery and electrolyte rebalancing method thereof |
| US20150303504A1 (en) * | 2014-04-21 | 2015-10-22 | Unienergy Technologies, Llc | Methods for determining and/or adjusting redox-active element concentrations in redox flow batteries |
| CN104181158A (en) * | 2014-08-22 | 2014-12-03 | 武钢集团昆明钢铁股份有限公司 | Method for measuring concentration of tetravalent and pentavalent vanadium ions in vanadium battery electrolyte |
| CN104614678A (en) * | 2015-01-21 | 2015-05-13 | 哈尔滨工业大学 | Online detection device and method of battery electrode level in lead-acid storage battery inner chemosynthesis process |
| CN105388127A (en) * | 2015-10-30 | 2016-03-09 | 清华大学深圳研究生院 | Online detecting method and system for concentration of all ions of all-vanadium redox flow battery |
| CN105702997A (en) * | 2016-04-11 | 2016-06-22 | 苏州久润能源科技有限公司 | Redox flow battery rebalance system, refox flow battery system and method for cycle capacity rebalance of redox flow battery |
Non-Patent Citations (2)
| Title |
|---|
| KITTIMA NGAMSAI: "Analysis and measurement of the electrolyte imbalance in a vanadium redox flow battery", 《JOURNAL OF POWER SOURCES》 * |
| 王熙俊: "钒电池电解液电位监测电极的研究", 《华北电力技术》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110534775A (en) * | 2019-09-03 | 2019-12-03 | 中国科学院金属研究所 | A kind of flow battery positive and negative anodes electrolyte migration control method |
| CN111551610A (en) * | 2020-04-07 | 2020-08-18 | 上海电气集团股份有限公司 | Vanadium electrolyte concentration testing method, miniature vanadium battery and vanadium electrolyte concentration testing device |
| CN114636747A (en) * | 2022-05-10 | 2022-06-17 | 上海柏中观澈智能科技有限公司 | Substance detection device and method and liquid quality monitoring equipment |
| CN114899460A (en) * | 2022-05-24 | 2022-08-12 | 寰泰储能科技股份有限公司 | Electrolyte vanadium concentration regulation and control method and device of all-vanadium liquid flow energy storage system |
| CN117393810A (en) * | 2023-12-12 | 2024-01-12 | 江苏美淼储能科技有限公司 | Method for recovering capacity of vanadium battery on line and inhibiting diffusion of vanadium ion across membrane on line |
| CN117393810B (en) * | 2023-12-12 | 2024-03-08 | 江苏美淼储能科技有限公司 | Method for recovering capacity of vanadium battery on line and inhibiting diffusion of vanadium ion across membrane on line |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109494388A (en) | 2019-03-19 |
| CN109473703B (en) | 2021-11-09 |
| CN109669142B (en) | 2021-12-31 |
| CN109473703A (en) | 2019-03-15 |
| CN109494388B (en) | 2021-11-09 |
| CN109546186B (en) | 2021-11-09 |
| CN109546186A (en) | 2019-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109669142A (en) | A kind of method and system for the migration of real-time monitoring all-vanadium flow battery vanadium | |
| US10388978B2 (en) | Methods for determining state of charge and calibrating reference electrodes in a redox flow battery | |
| Omosebi et al. | Continuous operation of membrane capacitive deionization cells assembled with dissimilar potential of zero charge electrode pairs | |
| CN106872905A (en) | A kind of full battery parameter acquisition methods of monomer lithium ion | |
| CN106353471B (en) | Biological oxygen demand sensor | |
| Madjarov et al. | Revisiting methods to characterize bioelectrochemical systems: the influence of uncompensated resistance (iRu-drop), double layer capacitance, and junction potential | |
| CN110411923B (en) | In-situ real-time monitoring device and method for submarine boundary layer based on natural potential measurement | |
| CN105929334B (en) | A kind of positive electrolyte for all-vanadiumredox flow battery state-of-charge assay method | |
| JP6196528B2 (en) | Dissolved hydrogen concentration measuring method and electrolyzed water generator | |
| CN109856037A (en) | A kind of measuring method of metal double polar plates long-time stability | |
| CN104535622A (en) | Monitoring method for sudden water quality change | |
| Loktionov et al. | Calibration-free coulometric sensors for operando electrolytes imbalance monitoring of vanadium redox flow battery | |
| EP3236248A1 (en) | Ionic conductivity test device, and test method using same | |
| CN216054872U (en) | System for monitoring and real-time regulating electrolyte component in lithium supplementing process, negative plate and battery | |
| JP4775523B1 (en) | Estimation apparatus and estimation method | |
| CN104849326B (en) | A kind of concrete reinforcement erosion condition judgement method | |
| Ji et al. | Temperature adaptability of the lead methanesulfonate flow battery | |
| CN112864427A (en) | Online monitoring device and method based on state of charge of flow battery | |
| Di Lorenzo et al. | A single chamber packed bed microbial fuel cell biosensor for measuring organic content of wastewater | |
| Han et al. | Modeling of interfacial resistance effects on the performance and efficiency for electrolyzer energy storage | |
| Vazquez-Arenas et al. | Comprehensive impedance model of cobalt deposition in sulfate solutions accounting for homogeneous reactions and adsorptive effects | |
| Wright et al. | L-Phenylalanine adsorption on Pt: electrochemical impedance spectroscopy and quartz crystal nanobalance studies | |
| CN207423754U (en) | A kind of ion exchange membrane performance tester | |
| RU2808661C1 (en) | Method for predicting specific capacity of graphite anodic material of lithium-ion battery | |
| Geisler et al. | Model based interpretation of coupled gas conversion and diffusion in SOFC-Anodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |