CN109346756A - A kind of flow battery system and its regeneration of electrolyte method of regeneration of electrolyte - Google Patents
A kind of flow battery system and its regeneration of electrolyte method of regeneration of electrolyte Download PDFInfo
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- CN109346756A CN109346756A CN201811418530.2A CN201811418530A CN109346756A CN 109346756 A CN109346756 A CN 109346756A CN 201811418530 A CN201811418530 A CN 201811418530A CN 109346756 A CN109346756 A CN 109346756A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 245
- 238000011069 regeneration method Methods 0.000 title claims abstract description 89
- 230000008929 regeneration Effects 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000012530 fluid Substances 0.000 claims abstract description 275
- 239000007788 liquid Substances 0.000 claims abstract description 87
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 30
- 238000005086 pumping Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 39
- 229910052720 vanadium Inorganic materials 0.000 claims description 29
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 27
- 238000005520 cutting process Methods 0.000 claims description 14
- 238000005868 electrolysis reaction Methods 0.000 claims description 13
- 238000013523 data management Methods 0.000 claims description 11
- 230000005611 electricity Effects 0.000 claims description 11
- 238000005259 measurement Methods 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 11
- 230000033116 oxidation-reduction process Effects 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000012544 monitoring process Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 238000012423 maintenance Methods 0.000 abstract description 9
- 230000001172 regenerating effect Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 description 8
- 238000004146 energy storage Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000007726 management method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
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
- H01M8/18—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
-
- 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
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
-
- 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
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
-
- 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
- H01M8/04276—Arrangements for managing the electrolyte stream, e.g. heat exchange
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The present invention a kind of flow battery system and its regeneration of electrolyte method of regeneration of electrolyte, the battery system include regeneration of electrolyte system and battery system, and battery system includes: for receiving several positive fluid reservoirs from pile discharge anode electrolyte；And for receiving several cathode fluid reservoirs from pile discharge electrolyte liquid；Regeneration of electrolyte system includes: the mixed flow container for receiving the electrolyte liquid that the anode electrolyte being discharged from several positive fluid reservoirs and several cathode fluid reservoirs are discharged；For receiving the regeneration of electrolyte module from mixed flow container discharge mixed electrolytic solution, after regeneration of electrolyte module carries out valence state adjustment to mixed electrolytic solution, the mixed electrolytic solution in mixed flow container is sent by pumping to several positive fluid reservoirs and several cathode fluid reservoirs.Electrolyte service life can be improved in flow battery system of the invention, reduces and carries out maintenance bring high maintenance cost using replacement electrolyte, regenerative system is integrated in mobile cabinet, the mobile operation of realization.
Description
Technical field
The present invention relates to a kind of flow battery field more particularly to the flow battery systems and its electricity of a kind of regeneration of electrolyte
Solve liquid regeneration method.
Background technique
All-vanadium flow battery has the outstanding advantages such as tight security and long-life as a kind of extensive energy-storage battery,
Demonstration Application is constantly carried out in field of new energy generation；In recent years, all-vanadium flow battery is because it is excellent in Demonstration Application
It more shows and has started gradually commercial applications.
Electric energy is converted into chemical energy storage in the electrolytic solution when vanadium flow battery charges, and when needed converts chemical energy to
Power output meets power demand；Vanadium flow battery positive and negative anodes electrolyte needs are separated by diaphragm, to hinder positive and negative anodes electrolyte
Both contacts contact mainly cause self discharge, need proton to shuttle in diaphragm to be connected to entire battery but then, because
This is other than requiring diaphragm material to have excellent chemical stability, it is also necessary to which diaphragm is conducive to the transmitting of proton, to reduce electricity
Pond internal resistance.
Present commercialized diaphragm material is perfluoro sulfonic acid membrane, and not only corrosion resistance is strong for this amberplex, Ke Yi
The contact of positive and negative anodes electrolyte is hindered to a certain extent, but also is had good conductive property；But in battery charging and discharging mistake
Cheng Zhong, by the effect of ion concentration differences and electric field various in positive and negative anodes electrolyte, vanadium ion in positive and negative anodes electrolyte and
Hydrogen ion carries different amounts of hydrone and passes through the other pole of diaphragm arrival, causes self discharge, and cause battery electrolyte that can produce
Raw volume change and concentration variation eventually lead to effective active electricity in electrolyte and cause capacity attenuation to concentration reduction；In addition, filling
There is also a small amount of side reactions in discharge process, and the reason of lead to vanadium redox flow battery electrolyte capacity attenuation；Therefore full vanadium
The electrolyte of flow battery, which needs to regularly replace or carry out " regeneration ", just can guarantee that the stablizing for capacity of system exports.
Patent CN 103117407A discloses a kind of mobile V electrolyte preparation facilities and V electrolyte preparation method,
A kind of mobile electrolyte preparation equipment of the Patent design, can save the expense of electrolyte long-distance transport and avoid long-distance
Potential risk of leakage in transportational process；Device and raw material solid can be transported to the project implementation, then carry out electrolyte life
Produce manufacture；But patent be not directed to the capacity attenuation generated in electrolyte use process is adjusted or it is regenerated in
Hold.
Patent CN 202996970U discloses a kind of V electrolyte preparation facilities of practical simplicity, and the patent is using electrolysis
Method prepares electrolyte, and patent key content is electrolyte preparation facilities；Do not cover to the capacity generated in electrolyte use process
Decaying is adjusted or regenerated content.
Patent 200810012119.5 discloses a kind of preparation of vanadium battery solution or the method for capacity regulating and its dedicated
Device, which prepares electrolyte of vanadium redox battery using electrolysis mode, and has in line or offline to the electrolyte after using and carry out
The function of capacity regulating, but the patent is not directed to movable operation, is also not directed to full-automatic operation.
To sum up, the generally existing following problems of regeneration of electrolyte system of existing vanadium cell: 1. are not directed to use electrolyte
The capacity attenuation generated in the process is adjusted or regenerated content；2. regeneration of electrolyte system is irremovable, do not automate
Operation.
Therefore, it is not directed to for the regeneration of electrolyte system of existing vanadium cell to the capacity generated in electrolyte use process
Decaying be adjusted or regenerated content and regeneration of electrolyte system it is irremovable, not the problems such as automated job, become
Those skilled in the art's technical problem urgently to be resolved.
Summary of the invention
The present invention is to solve the regeneration of electrolyte system of existing vanadium cell to be not directed to generate in electrolyte use process
Capacity attenuation be adjusted or regenerated content and regeneration of electrolyte system it is irremovable, not the problems such as automated job,
Provide the flow battery system and its regeneration of electrolyte method of regeneration of electrolyte.
To achieve the above object, the invention adopts the following technical scheme:
A kind of flow battery system of regeneration of electrolyte, including regeneration of electrolyte system and battery system are provided, it is described
Battery system includes:
For receiving several positive fluid reservoirs from pile discharge anode electrolyte；And
For receiving several cathode fluid reservoirs from pile discharge electrolyte liquid；
The regeneration of electrolyte system includes:
For receiving the anode electrolyte being discharged from several positive fluid reservoirs and several cathode fluid reservoir discharges
Electrolyte liquid and mixed flow container that the anode electrolyte and the electrolyte liquid are mixed；
For receiving from the mixed flow container discharge mixed electrolytic solution and carrying out to the mixed electrolytic solution electricity of valence state adjustment
Liquid regeneration module is solved, after the regeneration of electrolyte module carries out valence state adjustment to the mixed electrolytic solution, in the mixed flow container
The mixed electrolytic solution is sent by pumping to several positive fluid reservoirs and several cathode fluid reservoirs.
Further, the regeneration of electrolyte module includes that the mixed electrolytic solution is discharged for receiving from the mixed flow container
And the electrolytic cell of valence state adjustment is carried out to the mixed electrolytic solution and provides the anode of anolyte for electrolytic cell circulation
Fluid reservoir.
Further, the mixed flow container, electrolytic cell and anode fluid reservoir are set in mobile cabinet.
Further, in the pipeline between several positive fluid reservoirs and several cathode fluid reservoirs and the pile
Equipped with sensor, the sensor is connect by cable with data management platform.
Provide a kind of regeneration of electrolyte method of flow battery system, comprising the following steps:
Step 1: the pipeline between several positive fluid reservoirs of cutting and several cathode fluid reservoirs and the pile
Or cut off pipeline between at least one described positive fluid reservoir and at least one cathode fluid reservoir and the pile；
Step 2: by the cathode in the anode electrolyte and several cathode fluid reservoirs in several positive fluid reservoirs
Electrolyte is discharged into the mixed flow container several positive liquid storages that carries out mixed liquid or will be not connected in step 1 with the pile
The electrolyte liquid in anode electrolyte and several cathode fluid reservoirs in tank, which is discharged into the mixed flow container, carries out mixed liquid, mixes
After the completion of liquid, the pipeline between the mixed flow container and several positive fluid reservoirs and several cathode fluid reservoirs is cut off, together
When the oxidation-reduction potential of solution in the mixed flow container is measured, obtain oxidation-reduction potential EN, and by ENFormula is substituted into obtain
The concentration proportion R of trivalent vanadium and tetravalence vanadium in the solutionNAnd electrolysis time t；
Step 3: the pipeline between the connection mixed flow container and regeneration of electrolyte module realizes the circulation conveying of electrolyte；
Step 4: after carrying out electroreduction to the electrolyte according to the electrolysis time t acquired in step 2, cutting
Pipeline between the mixed flow container and regeneration of electrolyte module, and it is connected to the mixed flow container and several positive fluid reservoirs simultaneously
If being not connected in the pipeline or the connection mixed flow container and step 1 between several cathode fluid reservoirs with the pile
The pipeline between the positive fluid reservoir and several cathode fluid reservoirs is done, if the solution in the mixed flow container is discharged by pump
Do several anodes being not connected in the positive fluid reservoir and several cathode fluid reservoirs or step 1 with the pile
Fluid reservoir and several cathode fluid reservoirs；
Step 5: to the cathode in the anode electrolyte and several cathode fluid reservoirs in several positive fluid reservoirs
The anode electrolyte in several positive fluid reservoirs that is not connected in electrolyte or step 1 with the pile and several described
After electrolyte liquid in cathode fluid reservoir reaches required volume, cut off the mixed flow container and several positive fluid reservoirs and
Pipeline between several cathode fluid reservoirs or the cutting mixed flow container in step 1 with not connected several of the pile
Pipeline between the anode fluid reservoir and several cathode fluid reservoirs, while being connected to several positive fluid reservoirs and several
Pipeline between the cathode fluid reservoir and the pile, anode electrolyte in several positive fluid reservoirs and several described
Electrolyte liquid in cathode fluid reservoir is discharged into the pile by pump.
Further, flow container is mixed described in step 2 during mixed liquid, and ORP value is carried out to the solution in the mixed flow container
Measurement, goal-selling voltage Y work as EN-EN-1When≤Y, mixes liquid and complete；The ENFor the ORP current potential of n-th measurement, EN-1For N-
The ORP current potential of 1 measurement.
Further, several positive fluid reservoirs and several cathode fluid reservoirs and institute are being cut off described in step 1
It states the pipeline between pile or cuts off at least one positive fluid reservoir and at least one described cathode fluid reservoir and the electricity
Before pipeline between heap, the pipeline being connected between pile and several cathode fluid reservoirs of several positive fluid reservoirs is described
Solution in pile is sent by pumping to several positive fluid reservoirs and several cathode fluid reservoirs.
Further, mixed described in step 4 solution in flow container by metering pump be discharged into several positive fluid reservoirs with
Several cathode fluid reservoirs are discharged into several positive fluid reservoirs being not connected in step 1 with the pile and several institutes
Cathode fluid reservoir is stated, anode electrolyte and several cathode fluid reservoirs in several positive fluid reservoirs of cmf record are passed through
Anode electrolyte and several in several positive fluid reservoirs being not connected in interior electrolyte liquid or step 1 with the pile
The volume of electrolyte liquid and anode electrolyte and several institutes in several positive fluid reservoirs are kept in the cathode fluid reservoir
State anode in several positive fluid reservoirs being not connected in electrolyte liquid in cathode fluid reservoir or step 1 with the pile
Electrolyte is consistent with the volume of electrolyte liquid in several cathode fluid reservoirs.
Further, to the anode electrolyte and several cathode liquid storages in several positive fluid reservoirs in step 5
After electrolyte liquid in tank reaches required volume, inert gas is injected into the mixed flow container and is sealed processing.
Further, several positive fluid reservoirs and several cathode fluid reservoirs and the pile are connected in step 5
Between the pipeline, sensor is equipped in the pipeline, the sensor is connect by cable with data management platform, described
Data management platform passes through in the sensor monitoring step five from several positive fluid reservoirs and several cathode liquid storages
Tank is delivered to the ORP current potential of the pile electrolyte.
The present invention by adopting the above technical scheme, compared with prior art, has the following technical effect that
(1) regeneration that V electrolyte can be achieved, improves electrolyte service life, reduces and is safeguarded using replacement electrolyte
Bring high maintenance cost；
(2) regenerative system is integrated in mobile cabinet, mobile operation may be implemented, therefore for large-scale vanadium fluid flow energy storage system
The case where mating more storage tanks, can not only carry out regeneration of electrolyte offline, can also realize and work online, and not influence energy-storage system fortune
Row；
(3) regenerative system is integrated in mobile cabinet, mobile operation may be implemented, it can be to avoid every set vanadium fluid flow energy storage system
System all leads to increased costs with dedicated regenerative system, hence it is evident that reduces the regeneration of electrolyte of the vanadium fluid flow energy storage system of dispersed distribution
Cost；
(4) present invention can acquire information by sensor and feed back to management system, can be to the regeneration of V electrolyte
Work carry out Intellectualized monitoring, high degree of automation, reduce electrolyte maintenance work for manpower demand, reduce maintenance at
This；
(5) present invention is realized and is controlled the volume and concentration of positive fluid reservoir and cathode fluid reservoir, while realization pair
The control of electrolyte valence state.
Detailed description of the invention
Fig. 1 is the arrangement connection schematic diagram of the flow battery system of regeneration of electrolyte of the present invention；
Fig. 2 is the flow battery system of regeneration of electrolyte of the present invention and the arrangement connection schematic diagram of mobile cabinet；
Fig. 3 is the flow battery system of regeneration of electrolyte of the present invention using the cloth of multiple positive fluid reservoirs and cathode fluid reservoir
Set connection schematic diagram；
Fig. 4 is the work flow diagram of the flow battery system of regeneration of electrolyte of the present invention；
Wherein, each appended drawing reference are as follows:
1- pile, 2- anode fluid reservoir, 3- cathode fluid reservoir, 4- mix flow container, 5- electrolytic cell, 6- anode fluid reservoir, 7- shifting
Dynamic cabinet, 8- sensor, 9- data management platform, 10- regeneration of electrolyte module.
Specific embodiment
The present invention is described in more detail below by specific embodiment, for a better understanding of the present invention,
But following embodiments are not intended to limit the scope of the invention.
Embodiment 1
As shown in Figure 1, present embodiments providing a kind of flow battery system of regeneration of electrolyte, including regeneration of electrolyte system
System and battery system, the battery system include:
For receiving the positive fluid reservoir 2 that anode electrolyte is discharged from pile 1；And
For receiving the cathode fluid reservoir 3 that electrolyte liquid is discharged from pile 1；
Regeneration of electrolyte system includes:
For receiving the electrolyte liquid of the anode electrolyte being discharged from positive fluid reservoir 2 and the discharge of cathode fluid reservoir 3 simultaneously
The mixed flow container 4 that anode electrolyte and electrolyte liquid electrolyte are mixed；
For receiving the regeneration of electrolyte that mixed electrolytic solution is discharged from mixed flow container 4 and carries out valence state adjustment to mixed electrolytic solution
Module 10, after regeneration of electrolyte module 10 carries out valence state adjustment to mixed electrolytic solution, the mixed electrolytic solution in mixed flow container 4 passes through pump
It send to positive fluid reservoir 2 and cathode fluid reservoir 3.
The present embodiment provides a kind of regeneration of electrolyte method according to the flow battery system of above-mentioned regeneration of electrolyte, including
Following steps:
Step 1: cutting off the pipeline between positive fluid reservoir 2 and cathode fluid reservoir 3 and pile 4；
Step 2: the electrolyte liquid in the anode electrolyte and cathode fluid reservoir 3 in positive fluid reservoir 2 is discharged into mixed liquid
Mixed liquid is carried out in tank 4, after the completion of mixing liquid, cuts off the pipeline between mixed flow container 4 and positive fluid reservoir 2 and cathode fluid reservoir 3, simultaneously
The oxidation-reduction potential of solution in mixed flow container 4 is measured, oxidation-reduction potential E is obtainedN, and by ENIt substitutes into formula and obtains solution
The concentration proportion R of middle trivalent vanadium and tetravalence vanadiumNAnd electrolysis time t；
Step 3: the pipeline being connected between mixed flow container 4 and regeneration of electrolyte module 10 realizes the circulation conveying of electrolyte；
Step 4: cutting off mixed flow container 4 after carrying out electroreduction to electrolyte according to the electrolysis time t acquired in step 2
With the pipeline between regeneration of electrolyte module 10, and it is connected between mixed flow container 4 and positive fluid reservoir 2 and cathode fluid reservoir 3 simultaneously
Pipeline, the solution in mixed flow container 4 is discharged into positive fluid reservoir 2 and cathode fluid reservoir 3 by pump；
Step 5: needed for reaching to the electrolyte liquid in the anode electrolyte and cathode fluid reservoir 3 in positive fluid reservoir 2
After volume, the pipeline between mixed flow container 4 and positive fluid reservoir 2 and cathode fluid reservoir 3 is cut off, while being connected to positive fluid reservoir 2
Pipeline between cathode fluid reservoir 3 and pile 1, the cathode in anode electrolyte and cathode fluid reservoir 3 in positive fluid reservoir 2
Electrolyte is discharged into pile 1 by pump.
The one side of the present embodiment, such as Fig. 1, shown in 4, formula in step 2 are as follows:
EN=E0-0.059ln(V3+/V4+)；
RN=V3+/V4+；
Q=I*t=n*F*m；
N=(RN-1)/2；
M=2V0M0；
T=[FV0M0(RN-1)]/I；
Wherein E0For constant, RNFor the concentration proportion of trivalent vanadium in solution and tetravalence vanadium, ENTo measure oxidation in step 3 also
Former current potential, V0For the initial volume of solution in positive fluid reservoir 2 and cathode fluid reservoir 3, M0For positive fluid reservoir 2 and cathode liquid storage
Initial concentration solution in tank 3.
The one side of the present embodiment, such as Fig. 1 mix flow container 4 during mixed liquid, in mixed flow container 4 shown in 4, in step 2
Solution carry out ORP value measurement, goal-selling voltage Y works as EN-EN-1When≤Y, mixes liquid and complete；ENFor the ORP electricity of n-th measurement
Position, EN-1The ORP current potential measured for the N-1 times.
The one side of the present embodiment, e.g., shown in Isosorbide-5-Nitrae, in step 1 cut off positive fluid reservoir 2 and cathode fluid reservoir 3 with
Before pipeline between pile 4, the pipeline being connected between pile 1 and positive fluid reservoir 2 and cathode fluid reservoir 3, the solution in pile 1
It is sent by pumping to positive fluid reservoir 2 and several cathode fluid reservoirs 3.
The one side of the present embodiment, e.g., the solution mixed in flow container 4 shown in Isosorbide-5-Nitrae, in step 4 are discharged into anode by metering pump
Fluid reservoir 2 and cathode fluid reservoir 3, by anode electrolyte and cathode fluid reservoir 3 in several positive fluid reservoirs 2 of cmf record
The volume of electrolyte liquid and the volume for keeping electrolyte liquid in anode electrolyte and cathode fluid reservoir 3 in positive fluid reservoir 2
Unanimously.
The one side of the present embodiment, e.g., shown in Isosorbide-5-Nitrae, to the anode electrolyte and cathode in positive fluid reservoir 2 in step 5
After electrolyte liquid in fluid reservoir 3 reaches required volume, inert gas is injected into mixed flow container 4 and is sealed processing.
Embodiment 2
As shown in Fig. 2, present embodiments providing a kind of flow battery system of regeneration of electrolyte, including regeneration of electrolyte system
System and battery system, battery system include:
For receiving the positive fluid reservoir 2 that anode electrolyte is discharged from pile 1；And
For receiving the cathode fluid reservoir 3 that electrolyte liquid is discharged from pile 1；
Regeneration of electrolyte system includes:
For receiving the electrolyte liquid of the anode electrolyte being discharged from positive fluid reservoir 2 and the discharge of cathode fluid reservoir 3 simultaneously
The mixed flow container 4 that anode electrolyte and electrolyte liquid are mixed；
For receiving the regeneration of electrolyte that mixed electrolytic solution is discharged from mixed flow container 4 and carries out valence state adjustment to mixed electrolytic solution
Module 10, after regeneration of electrolyte module 10 carries out valence state adjustment to mixed electrolytic solution, the mixed electrolytic solution in mixed flow container 4 passes through pump
It send to positive fluid reservoir 2 and cathode fluid reservoir 3.
The one side of the present embodiment, such as Fig. 2, shown in 4, regeneration of electrolyte module 10 includes for receiving from mixed 4 row of flow container
Out mixed electrolytic solution and to mixed electrolytic solution carry out valence state adjustment electrolytic cell 5 and for electrolytic cell 5 recycle anolyte is provided
Anode fluid reservoir 6.
The one side of the present embodiment, such as Fig. 2 shown in 4, mix flow container 4, electrolytic cell 5 and anode fluid reservoir 6 and are set to movement
In cabinet 7.
The one side of the present embodiment, such as Fig. 2, several anode fluid reservoirs 2 and several cathode fluid reservoirs 3 and pile 1 shown in 4 it
Between pipeline in be equipped with sensor 8, sensor 8 is connect by cable with data management platform 9, and data management platform 9 passes through biography
Sensor 8 monitors several positive fluid reservoirs 2 and several cathode fluid reservoirs 3 are delivered to the ORP current potential of 1 electrolyte of pile.
The present embodiment provides a kind of regeneration of electrolyte method according to the flow battery system of above-mentioned regeneration of electrolyte, including
Following steps:
Step 1: cutting off the pipeline between positive fluid reservoir 2 and cathode fluid reservoir 3 and pile 4；
Step 2: the electrolyte liquid in the anode electrolyte and cathode fluid reservoir 3 in positive fluid reservoir 2 is discharged into mixed liquid
Mixed liquid is carried out in tank 4, after the completion of mixing liquid, cuts off the pipeline between mixed flow container 4 and positive fluid reservoir 2 and cathode fluid reservoir 3, simultaneously
The oxidation-reduction potential of solution in mixed flow container 4 is measured, oxidation-reduction potential E is obtainedN, and by ENIt substitutes into formula and obtains solution
The concentration proportion R of middle trivalent vanadium and tetravalence vanadiumNAnd electrolysis time t；
Step 3: the pipeline being connected between mixed flow container 4 and regeneration of electrolyte module 10 realizes the circulation conveying of electrolyte；
Step 4: cutting off mixed flow container 4 after carrying out electroreduction to electrolyte according to the electrolysis time t acquired in step 2
With the pipeline between regeneration of electrolyte module 10, and it is connected between mixed flow container 4 and positive fluid reservoir 2 and cathode fluid reservoir 3 simultaneously
Pipeline, the solution in mixed flow container 4 is discharged into positive fluid reservoir 2 and cathode fluid reservoir 3 by pump；
Step 5: reaching required volume to electrolyte liquid in anode electrolyte in positive fluid reservoir 2 and cathode fluid reservoir 3
After amount, the pipeline between mixed flow container 4 and positive fluid reservoir 2 and cathode fluid reservoir 3 is cut off, while being connected to positive fluid reservoir 2 and bearing
Pipeline between pole fluid reservoir 3 and pile 1, electrolyte liquid is logical in anode electrolyte and cathode fluid reservoir 3 in positive fluid reservoir 2
Pump is crossed to be discharged into pile 1.
The one side of the present embodiment, such as Fig. 2, shown in 4, formula in step 2 are as follows:
EN=E0-0.059ln(V3+/V4+)；
RN=V3+/V4+；
Q=I*t=n*F*m；
N=(RN-1)/2；
M=2V0M0；
T=[FV0M0(RN-1)]/I；
Wherein E0For constant, RNFor the concentration proportion of trivalent vanadium in solution and tetravalence vanadium, ENTo measure oxidation in step 3 also
Former current potential, V0For the initial volume of solution in positive fluid reservoir 2 and cathode fluid reservoir 3, M0For positive fluid reservoir 2 and cathode liquid storage
Initial concentration solution in tank 3.
The one side of the present embodiment, such as Fig. 2 mix flow container 4 during mixed liquid, in mixed flow container 4 shown in 4, in step 2
Solution carry out ORP value measurement, goal-selling voltage Y works as EN-EN-1When≤Y, mixes liquid and complete；ENFor the ORP electricity of n-th measurement
Position, EN-1The ORP current potential measured for the N-1 times.
The one side of the present embodiment, such as Fig. 2, shown in 4, in step 1 cut off positive fluid reservoir 2 and cathode fluid reservoir 3 with
Before pipeline between pile 4, the pipeline being connected between pile 1 and positive fluid reservoir 2 and cathode fluid reservoir 3, the solution in pile 1
It is sent by pumping to positive fluid reservoir 2 and cathode fluid reservoir 3.
The one side of the present embodiment, such as Fig. 2, the solution mixed in flow container 4 shown in 4, in step 4 are discharged into just by metering pump
Pole fluid reservoir 2 and cathode fluid reservoir 3, by being born in anode electrolyte in cmf record anode fluid reservoir 2 and cathode fluid reservoir 3
The volume of pole electrolyte and the volume one for keeping electrolyte liquid in anode electrolyte and cathode fluid reservoir 3 in positive fluid reservoir 2
It causes.
The one side of the present embodiment, such as Fig. 2, shown in 4, to anode electrolyte in positive fluid reservoir 2 and negative in step 5
After electrolyte liquid in pole fluid reservoir 3 reaches required volume, inert gas is injected into mixed flow container 4 and is sealed processing.
The one side of the present embodiment, such as Fig. 2 are connected to positive fluid reservoir 2 and cathode fluid reservoir 3 and electricity shown in 4, in step 5
Pipeline between heap 1, pipeline is interior to be equipped with sensor 8, and sensor 8 is connect by cable with data management platform 9, and data management is flat
Platform 9 is electric by the ORP for being delivered to 1 electrolyte of pile from positive fluid reservoir 2 and cathode fluid reservoir 3 in 8 monitoring step five of sensor
Position, to control the ORP current potential of 3 electrolyte inside of positive fluid reservoir 2 and cathode fluid reservoir.
Embodiment 3
As shown in figure 3, present embodiments providing a kind of flow battery system of regeneration of electrolyte, including regeneration of electrolyte system
System and battery system, battery system include:
For receiving two positive fluid reservoirs 2 that anode electrolyte is discharged from pile 1；And
For receiving two cathode fluid reservoirs 3 that electrolyte liquid is discharged from pile 1；
Regeneration of electrolyte system includes:
Anode electrolyte and a discharge electrolyte of cathode fluid reservoir 3 is discharged for receiving from a positive fluid reservoir 2
Liquid and the mixed flow container 4 that anode electrolyte and electrolyte liquid are mixed；
For receiving the regeneration of electrolyte that mixed electrolytic solution is discharged from mixed flow container 4 and carries out valence state adjustment to mixed electrolytic solution
Module 10, after regeneration of electrolyte module 10 carries out valence state adjustment to mixed electrolytic solution, the mixed electrolytic solution in mixed flow container 4 passes through pump
Most mixed flow container 4 is sent to provide the positive fluid reservoir 2 and a cathode fluid reservoir 3 of electrolyte.
The present embodiment provides a kind of regeneration of electrolyte method according to the flow battery system of above-mentioned regeneration of electrolyte, including
Following steps:
Step 1: the pipeline between cutting one positive fluid reservoir 2 and a cathode fluid reservoir 3 and pile 4；
Step 2: by a positive fluid reservoir 2 being not connected in step 1 with pile 4 anode electrolyte and one it is negative
Electrolyte liquid in pole fluid reservoir 3, which is discharged into mixed flow container 4, carries out mixed liquid, after the completion of mixing liquid, cuts off mixed flow container 4 and positive liquid storage
Pipeline between tank 2 and cathode fluid reservoir 3, while the oxidation-reduction potential of solution in mixed flow container 4 is measured, it must aoxidize also
Former current potential EN, and by ENIt substitutes into formula and obtains the concentration proportion R of trivalent vanadium and tetravalence vanadium in solutionNAnd electrolysis time t；
Step 3: the pipeline being connected between mixed flow container 4 and regeneration of electrolyte module 10 realizes the circulation conveying of electrolyte；
Step 4: cutting off mixed flow container 4 after carrying out electroreduction to electrolyte according to the electrolysis time t acquired in step 2
With the pipeline between regeneration of electrolyte module 10, and it is connected to mixed flow container 4 simultaneously be not connected in step 1 with pile 4 one just
Pipeline between pole fluid reservoir 2 and a cathode fluid reservoir 3, the solution mixed in flow container 4 are discharged into step 1 and pile 4 by pump
The positive fluid reservoir 2 of not connected one and a cathode fluid reservoir 3；
Step 5: anode electrolyte and a cathode in a positive fluid reservoir 2 being not connected in step 1 with pile 4
After electrolyte liquid in fluid reservoir 3 reaches required volume, one be not connected in mixed flow container 4 and step 1 with pile 4 is cut off
Pipeline between a anode fluid reservoir 2 and a cathode fluid reservoir 3, while being connected to two positive fluid reservoirs 2 and two cathode storages
Pipeline between flow container 3 and pile 1, the cathode in anode electrolyte and two cathode fluid reservoirs 3 in two positive fluid reservoirs 2
Electrolyte is discharged into pile 1 by pump.
The one side of the present embodiment, such as Fig. 2, shown in 4, formula in step 2 are as follows:
EN=E0-0.059ln(V3+/V4+)；
RN=V3+/V4+；
Q=I*t=n*F*m；
N=(RN-1)/2；
M=2V0M0；
T=[FV0M0(RN-1)]/I；
Wherein E0For constant, RNFor the concentration proportion of trivalent vanadium in solution and tetravalence vanadium, ENTo measure oxidation in step 3 also
Former current potential, V0For the initial volume of solution in positive fluid reservoir 2 and cathode fluid reservoir 3, M0For positive fluid reservoir 2 and cathode liquid storage
Initial concentration solution in tank 3.
The one side of the present embodiment mixes flow container 4 during mixed liquid, in mixed flow container 4 as shown in figures 3 and 4, in step 2
Solution carry out ORP value measurement, goal-selling voltage Y works as EN-EN-1When≤Y, mixes liquid and complete；ENFor the ORP electricity of n-th measurement
Position, EN-1The ORP current potential measured for the N-1 times.
The one side of the present embodiment, as shown in figures 3 and 4, in one positive fluid reservoir 2 of cutting and a cathode in step 1
Before pipeline between fluid reservoir 3 and pile 4, it is connected between pile 1 and two positive fluid reservoirs 2 and two cathode fluid reservoirs 3
Pipeline, the solution in pile 1 are sent by pumping to two positive fluid reservoirs 2 and two cathode fluid reservoirs 3.
The one side of the present embodiment, the solution mixed in flow container 4 as shown in figures 3 and 4, in step 4 are discharged into step by metering pump
In the positive fluid reservoir 2 and a cathode fluid reservoir 3 being not connected in rapid one with pile 4, pass through cmf record step 1
In in a positive fluid reservoir 2 being not connected with pile 4 in anode electrolyte and a cathode fluid reservoir 3 electrolyte liquid body
It accumulates and keeps in one be not connected in step 1 with pile 4 positive fluid reservoir 2 in anode electrolyte and a cathode fluid reservoir 3
The volume of electrolyte liquid is consistent.
The one side of the present embodiment, as shown in figures 3 and 4, in step 5 just to one not connected with pile 4 in step 1
After the electrolyte liquid in anode electrolyte and a cathode fluid reservoir 3 in pole fluid reservoir 2 reaches required volume, to mixed liquid
Injection inert gas is sealed processing in tank 4.
The present invention is not directed to for the regeneration of electrolyte system of existing vanadium cell to the appearance generated in electrolyte use process
Amount decaying be adjusted or regenerated content and regeneration of electrolyte system it is irremovable, not the problems such as automated job, this
The regeneration that V electrolyte can be achieved is invented, electrolyte service life is improved, reduces and maintenance bring is carried out using replacement electrolyte
High maintenance cost, regenerative system are integrated in mobile cabinet, and mobile operation may be implemented, information is acquired by sensor and is fed back
To management system, Intellectualized monitoring can be carried out to the reproduction operation of V electrolyte, high degree of automation reduces electrolyte maintenance
The demand to work for manpower reduces maintenance cost.
Above the flow battery system to regeneration of electrolyte of the present invention and its specific embodiment of regeneration of electrolyte method into
Detailed description is gone, but it is merely an example, the present invention is not restricted to particular embodiments described above.For this field
For technical staff, any equivalent modifications and substitutions to the present invention are also within the scope of the present invention.Therefore, not
It is detached from made equal transformation and modification under the spirit and scope of the present invention, all should be contained within the scope of the invention.
Claims (10)
1. a kind of flow battery system of regeneration of electrolyte, including regeneration of electrolyte system and battery system, which is characterized in that institute
Stating battery system includes:
For receiving several positive fluid reservoirs (2) from pile (1) discharge anode electrolyte；With
For receiving several cathode fluid reservoirs (3) from the pile (1) discharge electrolyte liquid；
The regeneration of electrolyte system includes:
For receiving the anode electrolyte being discharged from several positive fluid reservoirs (2) and several cathode fluid reservoir (3) rows
Electrolyte liquid out and the mixed flow container (4) that the anode electrolyte and the electrolyte liquid are mixed；With
For receiving from mixed flow container (4) the discharge mixed electrolytic solution and carrying out to the mixed electrolytic solution electrolysis of valence state adjustment
Liquid regeneration module (10), after the regeneration of electrolyte module (10) carries out valence state adjustment to the mixed electrolytic solution, the mixed liquid
The mixed electrolytic solution in tank (4) is sent by pumping to several positive fluid reservoirs (2) and several cathode fluid reservoirs
(3)。
2. the flow battery system of regeneration of electrolyte according to claim 1, which is characterized in that the regeneration of electrolyte mould
Block (10) includes for receiving the mixed electrolytic solution being discharged from the mixed flow container (4) and carrying out valence to the mixed electrolytic solution
The electrolytic cell (5) and provide the anode fluid reservoir (6) of anolyte for the electrolytic cell (5) circulation that state adjusts.
3. the flow battery system of regeneration of electrolyte according to claim 2, which is characterized in that the mixed flow container (4), electricity
Slot (5) and anode fluid reservoir (6) is solved to be set in mobile cabinet (7).
4. the flow battery system of regeneration of electrolyte according to claim 1, which is characterized in that several positive liquid storages
Sensor (8) are equipped in pipeline between tank (2) and several cathode fluid reservoirs (3) and the pile (1), the sensor
(8) it is connect by cable with data management platform (9).
5. a kind of regeneration of electrolyte method of the flow battery system as described in claim any one of 1-4, which is characterized in that including
Following steps:
Step 1: between several positive fluid reservoirs (2) of cutting and several cathode fluid reservoirs (3) and the pile (4)
Pipeline or cut off at least one positive fluid reservoir (2) and at least one described cathode fluid reservoir (3) and the pile (4)
Between pipeline；
Step 2: by negative in the anode electrolyte and several cathode fluid reservoirs (3) in several positive fluid reservoirs (2)
Pole electrolyte, which is discharged into the mixed flow container (4), carries out mixed liquid or several described by what is be not connected in step 1 with the pile (4)
The electrolyte liquid in anode electrolyte and several cathode fluid reservoirs (3) in positive fluid reservoir (2) is discharged into the mixed liquid
Mixed liquid is carried out in tank (4), after the completion of mixing liquid, cuts off the mixed flow container (4) and several anode fluid reservoirs (2) and several described
Pipeline between cathode fluid reservoir (3), while the oxidation-reduction potential of the interior solution of the mixed flow container (4) is measured, obtain oxygen
Change reduction potential EN, and by ENIt substitutes into formula and obtains the concentration proportion R of trivalent vanadium and tetravalence vanadium in the solutionNAnd when electrolysis
Between t；
Step 3: the pipeline between the connection mixed flow container (4) and regeneration of electrolyte module (10) realizes that the circulation of electrolyte is defeated
It send；
Step 4: after carrying out electroreduction to the electrolyte according to the electrolysis time t acquired in step 2, described in cutting
Pipeline between mixed flow container (4) and regeneration of electrolyte module (10), and it is connected to the mixed flow container (4) and several anodes simultaneously
Pipeline between fluid reservoir (2) and several cathode fluid reservoirs (3) or the connection mixed flow container (4) in step 1 with it is described
Pipeline between pile (4) not connected several positive fluid reservoirs (2) and several cathode fluid reservoirs (3), it is described mixed
Solution in flow container (4) is discharged into several positive fluid reservoirs (2) and several cathode fluid reservoirs (3) or step 1 by pump
In several positive fluid reservoirs (2) and several cathode fluid reservoirs (3) that are not connected with the pile (4)；
Step 5: to negative in the anode electrolyte and several cathode fluid reservoirs (3) in several positive fluid reservoirs (2)
The anode electrolyte in several positive fluid reservoirs (2) that is not connected in pole electrolyte or step 1 with the pile (4) and
After electrolyte liquid in several cathode fluid reservoirs (3) reaches required volume, the mixed flow container (4) and several institutes are cut off
It states in pipeline or the cutting mixed flow container (4) and the step 1 between positive fluid reservoir (2) and several cathode fluid reservoirs (3)
Pipeline between several positive fluid reservoirs (2) and several cathode fluid reservoirs (3) not connected with the pile (4),
The pipeline being connected between several positive fluid reservoirs (2) and several cathode fluid reservoirs (3) and the pile (1) simultaneously,
The electrolyte liquid in anode electrolyte and several cathode fluid reservoirs (3) in several positive fluid reservoirs (2) passes through
Pump is discharged into the pile (1).
6. regeneration of electrolyte method according to claim 5, which is characterized in that mix flow container (4) described in step 2 mixed
During liquid, ORP value measurement is carried out to the solution in the mixed flow container (4), goal-selling voltage Y works as EN-EN-1When≤Y, mix
Liquid is completed；The ENFor the ORP current potential of n-th measurement, EN-1The ORP current potential measured for the N-1 times.
7. regeneration of electrolyte method according to claim 4, which is characterized in that several described in cutting described in step 1
Pipeline between positive fluid reservoir (2) and several cathode fluid reservoirs (3) and the pile (4) is cut off described at least one
Before pipeline between positive fluid reservoir (2) and at least one cathode fluid reservoir (3) and the pile (4), it is connected to pile (1)
With the pipeline between several positive fluid reservoirs (2) and several cathode fluid reservoirs (3), solution in the pile (1)
It is sent by pumping to several positive fluid reservoirs (2) and several cathode fluid reservoirs (3).
8. regeneration of electrolyte method according to claim 5, which is characterized in that mixed in flow container (4) described in step 4
Solution is discharged into several positive fluid reservoirs (2) and several cathode fluid reservoirs (3) by metering pump or is discharged into step 1
Several positive fluid reservoirs (2) and several cathode fluid reservoirs (3) being not connected with the pile (4), pass through flowmeter
Record several positive fluid reservoir (2) interior anode electrolytes and the interior electrolyte liquid of several cathode fluid reservoirs (3) or step
Several positive interior anode electrolytes of fluid reservoir (2) being not connected in rapid one with the pile (4) and several cathode store up
The volume of the interior electrolyte liquid of flow container (3) simultaneously keeps the interior anode electrolyte of several positive fluid reservoirs (2) and several described negative
In several positive fluid reservoirs (2) being not connected in the interior electrolyte liquid of pole fluid reservoir (3) or step 1 with the pile (4)
Anode electrolyte is consistent with the volume of several interior electrolyte liquid of cathode fluid reservoir (3).
9. regeneration of electrolyte method according to claim 5, which is characterized in that several positive liquid storages in step 5
After the electrolyte liquid in anode electrolyte and several cathode fluid reservoirs (3) in tank (2) reaches required volume, to institute
It states injection inert gas in mixed flow container (4) and is sealed processing.
10. regeneration of electrolyte method according to claim 5, which is characterized in that be connected to several anodes in step 5
Sensor (8) are equipped in the pipeline between fluid reservoir (2) and several cathode fluid reservoirs (3) and the pile (1), institute
It states sensor (8) to connect by cable with data management platform (9), the data management platform (9) passes through the sensor (8)
The pile (1) electricity is delivered to from several positive fluid reservoirs (2) and several cathode fluid reservoirs (3) in monitoring step five
Solve the ORP current potential of liquid.
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