CN107959038A - A kind of flow battery pulsed charge-discharge system and method for improving electrolyte utilization rate - Google Patents
A kind of flow battery pulsed charge-discharge system and method for improving electrolyte utilization rate Download PDFInfo
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- CN107959038A CN107959038A CN201711105693.0A CN201711105693A CN107959038A CN 107959038 A CN107959038 A CN 107959038A CN 201711105693 A CN201711105693 A CN 201711105693A CN 107959038 A CN107959038 A CN 107959038A
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- 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
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- 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
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- 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
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- 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
- H01M8/04283—Supply means of electrolyte to or in matrix-fuel cells
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of flow battery pulsed charge-discharge system and method for improving electrolyte utilization rate, belong to new energy energy storage field.An intermittent pulse signal cut-off is being inputted to pulsed timed power switch, charge-discharge system is no longer constantly charged to the electrolyte in flow battery, but be transformed to intermittent charging.In the period do not charged, circulating pump still continuous service, until reaching charge cutoff voltage, completes charging process and simultaneously enters discharge process.In discharge process, also make pulsed timed power switch is intermittent to cut-off, keep the intermittent electric discharge of electrolyte, until reaching discharge cut-off voltage, complete discharge process.Thus a charge and discharge cycles are formed.Except the contradiction between balance concentration polarization and pump work can be reached in the present invention, moreover it is possible to reduce the difference of electrolyte state-of-charge between pile and fluid reservoir, improve the utilization rate of electrolyte.
Description
Technical field
The invention belongs to new energy energy storage field, and in particular to a kind of flow battery pulsed for improving electrolyte utilization rate
Charge-discharge system and method.
Background technology
In recent years, it is also all with day to the demand of the energy with the development of human being's production and the continuous improvement of living standard
Increase.However, limited non-regeneration energy can not ensure the needs of human kind sustainable development, traditional energy based on fossil energy
Source Supply Structure has become the bottleneck for restricting socio-economic development.Therefore, optimize energy source use structure, develop renewable new energy
Source, becomes the hot spot that the world pays close attention to and studies jointly.
However, the utilization of new energy is limited by time and external environment condition, cause its stability and continuity poor, at the same time
Also more serious impact can be produced to power grid.Therefore, it is necessary to configure corresponding energy storage device in network system, filled in the energy
Electric energy is stored when sufficient, is generated electricity by way of merging two or more grid systems when electricity lacks, adjusts the imbalance between supply and demand of the energy, realizes peak load shifting, and then realize energy
The efficient of source exports using with the electric energy of stable and continuous.
Extensive high-efficiency energy-storage technology is to realize the key technology that renewable energy power generation scale utilizes.Redox flow
Galvanic battery is to be most suitable for being applied to one of the extensive energy storage technology in renewable new energy field at present.Redox flow batteries
Concept proposed earliest by L.H.Thaller, in recent years, its research and develop, engineering and industrialization also constantly obtain it is important into
Exhibition, shows huge application prospect in extensive technical field of energy storage.It is different with traditional energy-storage system, oxidation solution galvanic electricity
The active material in pond is dissolved in its electrolyte, and is stored in exterior fluid reservoir.Traditional flow battery structure is by two circulations
Positive and negative anodes electrolyte is transferred to the pile region of battery by pump from fluid reservoir respectively, when electrolyte flows through electrode zone, in electrode
Occur to mutually convert process between chemical energy and electric energy on surface, so as to fulfill the mutual conversion between electric energy and chemical energy,
Achieve the purpose that energy storage.
The pile of flow battery overlaps assembling by several sections of or tens of section single batteries in the way of filter press.Each battery list
Member all includes two half-cells, it, which forms component, has：Solid electrode, bipolar plates, liquid flow frame and end plate.Between two half-cells
Amberplex is clipped, single battery is divided into positive and negative electrode two reaction zones domain, rising allows proton exchange, prevents other reactions
Ion and the effect of foreign ion migration.Solid electrode for electrochemical reaction carry out provide reacting environment, electrode area is got over
Greatly, discharge and recharge reaction speed is bigger, and corresponding power is also higher.Partition plate between two adjacent single batteries is known as double
Pole plate.Flow battery system is protected by pile, electrolyte, electrolyte fluid reservoir, circulating pump, pipeline, ancillary equipment instrument and detection
Protect equipment composition.Electrolyte fluid reservoir is respectively used to hold positive and negative anodes electrolyte, and is equipped with two circulating pumps and is used in closing
It is each half-cell unit transportation electrolyte in pipeline.During charging, the increase of the state-of-charge (SoC) of battery, during electric discharge, battery
State-of-charge (SoC) reduces.
In battery charge and discharge process, the amount of reactivity thing gradually reduces in electrolyte, especially in discharge and recharge latter stage,
Reactivity thing concentration is very low, and when discharge and recharge blanking voltage scope is higher, the confession of reactivity thing easily occurs in discharge and recharge latter stage
Should be insufficient, mass transfer can be caused to deteriorate, cause larger concentration polarization, reduce battery efficiency.To ensure the in liberal supply of reactant,
The minimum value that can obtain flow of electrolyte by theoretical calculation is：
In formula：I is charging and discharging currents, A；F is Faraday constant, about 96485C/mol；SoC is the charged shape of battery
State, can calculate and learn according to the active ion of question response in electrolyte and the ion concentration of generation.
The actual flow of electrolyte is：
Q=fac × Qmin
In formula：Fac is rate factor dimensionless constant.
But not The faster the better for the flow velocity of electrolyte, when reaching the certain flow rate upper limit, improving flow velocity cannot be further
Reduce the concentration polarization loss of battery or improve battery efficiency, pump work can be increased considerably on the contrary, consume unnecessary electric energy, it is right
The service life of whole battery system also has a certain impact.Therefore, in practical applications, it is 4~20 generally to take fac, dense to reconcile
Contradiction between difference polarization and pump work, keeps higher battery efficiency.
However, current flow optimization model only considered the contradiction between the concentration polarization of flow battery and pump work, neglect
The difference of the electrolyte state-of-charge between pile and storage tank is omited.Applicant is had found by studying, in flow battery discharge and recharge
During, the state-of-charge (SoC) of electrolyte will be different between pile and storage tank, especially in the case of low flow velocity
Difference between the two can be clearly.Such as in the case of the electrolyte of 1.6mol/L is used in all-vanadium flow battery, if
During flow rate coefficient fac=0.5, the state-of-charge maximum difference between storage tank and pile is up to more than 0.8mol/L.When
During the electrolyte outflow pile of highly charged state, the electrolyte of meeting state-of-charge low with storage tank mixes, and during this
Time difference can cause the state-of-charge of electrolyte in storage tank can the permanent state-of-charge for being less than electrolyte in pile.When flow velocity very
When small, difference will be clearly.Since the discharge and recharge blanking voltage of battery is all charged according to what is collected in pile
What state was judged, therefore, this species diversity will seriously affect the utilization rate of electrolyte.In other words, when electrolyte in pile
State-of-charge when being already higher than charge cutoff voltage, the state-of-charge of electrolyte is also very low in storage tank, this just has exhausted big portion
The electrolyte divided is not utilized, and in the case of high flow rate, such case can not be solved thoroughly.By
This, the method sought to reduce or eliminate electrolyte state-of-charge (SoC) difference between pile and storage tank seems particularly urgent.This hair
The bright method can not only improve the utilization rate of electrolyte under any rate conditions, can also in the case of low flow velocity energy
Enough current densities for improving charging, to improve the response performance of flow battery.
Traditional flow battery using two storage tanks the method for operation：First, added in positive and negative anodes electrolyte fluid reservoir
Isometric electrolyte, battery carry out charging process first after bringing into operation, positive and negative anodes electrolyte is entered by circulating pump respectively
The pile region of battery, and redox reaction occurs at the electrode surface, make the state-of-charge (SoC) of electrolyte increase, with
The increased electrolyte outflow pile of state-of-charge (SoC) afterwards, comes back in positive and negative anodes electrolyte fluid reservoir, with fluid reservoir respectively
In low state-of-charge (SoC) electrolyte mixing, the circulation of electrolyte is carried out with this, until the voltage in pile reach charging cut
Only voltage.Discharge process is then carried out, the state-of-charge (SoC) of electrolyte is gradually reduced, put until the voltage in pile reaches
Electric blanking voltage, completes a charge and discharge cycles.Under this method of operation, if flow velocity is too low, reactivity thing supplies in pile
Should be insufficient, concentration polarization increase causes battery efficiency to reduce, and flow velocity is excessive, can make the pump work of system increase, and can equally reduce
The efficiency of battery system.
In order to balance the contradiction between concentration polarization and pump work, current research be mostly by way of adjusting flow into
Row optimization.Related technical personnel further investigate, and following technology occur：
The patent of invention of Application No. CN201010210100.9 disclose a kind of all vanadium flow energy-storage battery system and its
Flow of electrolyte step control strategy, by different electrolytes temperature range, single battery voltage section, current density section into
Row is tested, and on the basis of the energy efficiency and power consumption that consider all vanadium flow energy-storage battery system, determines different electrolytes temperature
Section, single battery voltage section, the optimal flow of electrolyte of current density section are spent, and is adjusted and pumped by Inverter Based on Single Chip Microcomputer
Working frequency and flow, ensure all vanadium flow energy-storage battery system run under the flow of electrolyte of selection.
The patent of invention of Application No. CN201410746201.6 discloses a kind of all-vanadium redox flow battery system electrolysis liquid stream
Optimal control method is measured, by proposing a kind of control strategy of the segmentation increase flow of electrolyte in battery charge and discharge process,
In cell operation, the charging and discharging state value SOC that is gathered according to charging and discharging state monitor calculates the electrolysis liquid streams of needs
Amount, the working frequency of centrifugal pump is adjusted by frequency converter, ensures that all-vanadium redox flow battery system is run under the flow of selection.
However, above patent only pays attention to the contradiction reconciled between balance concentration polarization and pump work, electricity is had not focused on
The difference of electrolyte state-of-charge (SoC) between heap and fluid reservoir.Under higher flow velocity, this species diversity still no
To thoroughly solving.Also, this mode for adjusting flow is doomed to prevent flow battery system from being run under relatively low flow velocity,
There are certain pump work loss.At present, low-down current density can only be also taken in the state of low flow velocity, is ensured in pile
The supply of reactivity thing is unlikely to very few.
Also related technical personnel study the method for operation of pump.There is following technology：
The patent application of Application No. CN201410241236.4 is disclosed between a kind of fluid-flow pump of lithium ion flow battery
Knock off and make automatic controller, increase a fluid-flow pump discontinuous operation automatic controller for lithium ion flow battery system, it can be certainly
It is dynamic to judge lithium ion flow battery service condition, completely automatically make fluid-flow pump start and stop, discontinuous operation, makes lithium ion liquid
The positive and negative anodes suspension intermittent cyclic of galvanic battery, is just gone out after the completion of being reacted into battery plus-negative plate reaction chamber by circulation.It is this
Mode can reduce liquid stream pump operation time, reduce pump work.But this form is unable to the electrolyte that accuracy controlling enters pile every time
Volume, and need to judge that there are one in system automation operation every time into the reaction time needed for the electrolyte of pile
Fixed difficulty.
The patent application of Application No. CN201610801986.1 discloses a kind of flow battery current interrupters and adopts
With the flow battery of this current interrupters, flow battery current interrupters, electric current cutout are added on the outlet conduit of electric pump
Component is in intermittent flow by liquid stream by rotation mode, allows electrolyte to make electricity in intermittent sectional each pile of input
The electrolyte in liquid pipeline is solved into intermittent disconnection.What " current interrupters " described in this mode substantially also functioned to is " electricity
The effect of solution liquid intermittent cyclic ", but structure is relative complex, in pile for the monocell that electrolyte disconnects, equivalent to
Sacrifice the output power of monocell.
The content of the invention
It is an object of the invention to solve problems of the prior art, and propose a kind of raising electrolyte utilization rate
Flow battery pulsed charge-discharge system and method, in the conversion of flow battery energy energy, reduce between pile and storage tank
State-of-charge (SoC) difference, increases substantially the utilization rate of electrolyte.
Heretofore described flow battery pulsed charge-discharge system is the operation by improving battery charging and discharging system
Mode, except the contradiction between balance concentration polarization and pump work can be reached, moreover it is possible to reduce electrolyte lotus between pile and fluid reservoir
The difference of electricity condition (SoC), improves the utilization rate of electrolyte, and can be applied to current density more in the case of low flow velocity
In big occasion, there is the advantage that flow optimization and the optimizing operating mode pumped do not have.
Heretofore described flow battery pulsed charge-discharge system is to be achieved through the following technical solutions：
The flow battery pulsed charge-discharge system of electrolyte utilization rate is improved, its structure is as follows：Flow battery both sides
There is anode electrolyte inlet, electrolyte liquid inlet, anode electrolyte liquid outlet and electrolyte liquid on pile end plate
Liquid outlet, anode electrolyte inlet and anode electrolyte liquid outlet connect anode electrolyte fluid reservoir by infusion pipeline,
Form the circulation loop of anode electrolyte；Electrolyte liquid inlet is connected with electrolyte liquid liquid outlet by infusion pipeline
Electrolyte liquid fluid reservoir, forms the circulation loop of electrolyte liquid；It is both provided with the infusion pipeline for providing electricity
Solve the circulating pump of liquid conveying power；Agitating device is equipped with anode electrolyte fluid reservoir and electrolyte liquid fluid reservoir；Liquid stream
The external charge-discharge system of collector plate of battery, charge-discharge system includes battery charging and discharging detection device and pulsed Timing power supply is opened
Close, pulsed timed power switch is series in the charge-discharge circuit of battery charging and discharging detection device and collector plate, is filled for controlling
The intermittent break-make of discharge circuit.
Preferably, the pulsed timed power switch is connected with the computer for input pulse control signal.
Preferably, the agitating device is magnet rotor.
Preferably, the electric pile structure of flow battery is：It is clamped with some single-cell structure units between the PP plates of both sides, two
Pile end plate is respectively fixed with outside the PP plates of side.
Preferably, the flow battery is all-vanadium flow battery, zinc-bromine flow battery or Zn-Ni liquid battery.
Another object of the present invention is to provide a kind of method that electrolyte utilization rate is improved using said system, its step
It is as follows：
Isometric electrolyte is added in anode electrolyte fluid reservoir and electrolyte liquid fluid reservoir first, and in two storages
Agitating device is separately turned in flow container to mix the electrolyte in tank；Open the circulation pump, makes positive and negative anodes electrolyte in infusion pipeline
Middle flowing, is entered in pile by pile end plate, pile PP plates, anode electrolyte inlet, electrolyte liquid inlet respectively
Single-cell structure unit in, redox reaction occurs in monocell, makes the state-of-charge of electrolyte increase, then passes through respectively
Cross anode electrolyte liquid outlet and electrolyte liquid liquid outlet returned in anode electrolyte fluid reservoir and electrolyte liquid fluid reservoir,
Form circulation loop；In the theoretical charging interval and theoretical discharge time calculated according to the volume of positive and negative anodes electrolyte, it will charge
It is divided into some time input computer with discharge time, control pulsed timed power switch cut-offs state, fills battery
Discharging detection device exports the electric current of pulsed, and electrolyte obtains intermittent charging in pile；The charge and discharge within the pulse period
The period that electric detection means does not charge, the circulating pump of driving positive and negative anodes electrolyte circulation still keep operating；When external discharge and recharge
When the voltage that the collector plate of system collects battery has reached charge cutoff voltage, charging terminates, and starts discharge process, at this time
Discharge process, the voltage that battery is collected until the collector plate of external charge-discharge system have reached system with still keeping pulsed
During to discharge cut-off voltage, discharge process terminates, and completes a complete charge and discharge cycles.
Preferably, in each pulse period of charge or discharge, the charging interval is amounted to not less than the theoretical charging
Time, total discharge time are not less than the theoretical discharge time.
Preferably, charge cutoff voltage is arranged to 1.7V.
Preferably, discharge cut-off voltage is arranged to 0.8V.
Heretofore described flow battery pulsed charge-discharge system controls pulsed Timing power supply to open by computer
The closure of pass and disconnection, the electric current of battery charging and discharging detection device output pulsed are made with this, i.e.,：Beginning-charging-is shut down-is filled
Electricity-shutdown ... electric discharge-shutdown-electric discharge-shutdown-end.In stopping process, two 6 continuous runnings of circulating pump, reduce battery
The difference of electrolyte state-of-charge (SoC) between pile and fluid reservoir, reduces the concentration polarization between pile and fluid reservoir.Shut down
After process, pulsed timed power switch closure, system continues charge or discharge process.Finally end in discharge and recharge
When, the utilization rate of electrolyte can be effectively improved, especially in the case of low flow velocity, the utilization rate of electrolyte, which can obtain, significantly to be carried
Rise.
Compared with prior art, the present invention there are following features：First, the utilization rate of positive and negative anodes electrolyte dramatically increases,
Can be greatly lowered the difference of electrolyte state-of-charge (SoC) between battery pile and fluid reservoir, reduce pile and fluid reservoir it
Between concentration polarization.Second, the prolonged discharge and recharge of battery can be still kept in the case of low flow velocity, can be in low flow velocity
In the case of be applied to current density bigger occasion in, keep battery it is working properly.3rd, in the feelings that the volume of fluid reservoir is larger
It under condition, can guarantee that liquid energy is electrolysed in fluid reservoir keeps good uniformity, avoid electrolyte mixing is uneven from being brought to battery
Influence.
Brief description of the drawings
Fig. 1 is a kind of flow battery pulsed discharge and recharge system for improving electrolyte utilization rate in present invention specific implementation example
Unite basic schematic diagram.
Fig. 2 is anode electrolyte feed liquor, the liquid outlet schematic diagram of Fig. 1 described devices in the present invention.
Fig. 3 is electrolyte liquid feed liquor, the liquid outlet schematic diagram of Fig. 1 described devices in the present invention.
Fig. 4 is the electrolyte utilization rate of corresponding device of the present invention and conventional apparatus with the relation between flow rate β.
In figure：Pile end plate 1, pile PP plates 2, single-cell structure unit 3, infusion pipeline 4, anode electrolyte fluid reservoir 5,
Circulating pump 6, electrolyte liquid fluid reservoir 7, magnet rotor 8, battery charging and discharging detection device 9, pulsed timed power switch 10,
Computer 11, anode electrolyte liquid outlet 12, anode electrolyte inlet 13, collector plate 14, bolt hole 15, electrolyte liquid go out
Liquid mouth 16, electrolyte liquid inlet 17.
Embodiment
The present invention is further elaborated and illustrated with reference to the accompanying drawings and detailed description.Each implementation in the present invention
The technical characteristic of mode can carry out respective combination on the premise of not colliding with each other.
As shown in Figures 1 to 3, in embodiment, the flow battery pulsed charge-discharge system master of electrolyte utilization rate is improved
To be made of three parts, be broadly divided into the discharge and recharge system of the pile part of battery, the outer circulating section of electrolyte and battery
System (external power supply) part.Its critical piece includes pile end plate 1, PP plates 2, single-cell structure unit 3, infusion pipeline 4, cathode
Electrolyte fluid reservoir 5, circulating pump 6, electrolyte liquid fluid reservoir 7, magnet rotor 8, battery charging and discharging detection device 9, pulsed
Timed power switch 10, computer 11, anode electrolyte liquid outlet 12, anode electrolyte inlet 13, collector plate 14, bolt hole
15, electrolyte liquid liquid outlet 16, electrolyte liquid inlet 17.
The pile part of battery mainly (can use polyethylene material by pile end plate 1 (can use stainless steel end plate), PP plates 2
Material, for ensureing battery, pretightning force is evenly distributed everywhere) and several 3 structures of single-cell structure unit, it is circumferential on pile end plate 1
Bolt hole 15 is opened up to be used to be fastened and fixed.Multiple single-cell structure units 3 are clamped between both sides PP plates 2, are divided outside both sides PP plates 2
Pile end plate 1 is not fixed with.The quantity of single-cell structure unit 3 is unlimited.Each single-cell structure unit 3 can be divided into afflux again
Plate 14 (copper coin can be used, for gathering the charged state of monocell from bipolar plates and being converted into voltage signal, while also will be outer
The electric current for connecing power supply delivers into battery, controls the charge or discharge of battery), bipolar plates (graphite cake can be used, for distinguishing
The positive and negative anodes of electrolyte simultaneously conduct electric signal), liquid flow frame, gasket seal, electrode (graphite felt can be used, for for electrolyte
Electrochemical reaction provide active region), amberplex (Nafion117 cation-exchange membranes can be used, in battery just
Anode transmits hydrogen ion and hydrone, keeps the charge balance of battery) etc. critical piece.
There is anode electrolyte inlet 13, electrolyte liquid inlet 17, just on the pile end plate 1 of flow battery both sides
Pole electrolyte liquid outlet 12 and electrolyte liquid liquid outlet 16, anode electrolyte inlet 13 and anode electrolyte liquid outlet 12 are equal
Anode electrolyte fluid reservoir 5 is connected by infusion pipeline, forms the circulation loop of anode electrolyte；Electrolyte liquid inlet 17
Electrolyte liquid fluid reservoir 7 is connected by infusion pipeline with electrolyte liquid liquid outlet 16, forms the circulation of electrolyte liquid
Circuit.The circulating pump 6 for providing electrolyte conveying power is both provided with the infusion pipeline of cathode and anode, preferably using compacted
Dynamic circulating pump, realizes that flow is adjustable.Magnet rotor 8 is equipped with anode electrolyte fluid reservoir 5 and electrolyte liquid fluid reservoir 7,
For being stirred to electrolyte.The 14 external charge-discharge system of collector plate of flow battery, charge-discharge system include battery charge and discharge
Electric detection means 9 and pulsed timed power switch 10, battery charging and discharging detection device 9 are used for as power supply in circuit communication
The status information such as voltage, battery capacity at collector plate 14 can be detected in real time at the same time to 14 output current of collector plate.Circuit leads to
Disconnected is to be controlled by pulsed timed power switch 10 according to storage inside or the pulse signal being received externally, this implementation
Pulsed timed power switch 10 is realized using the time switch of PLC technology in example.Pulsed timed power switch 10 is connected
In the charge-discharge circuit of battery charging and discharging detection device and collector plate 14, pulsed timed power switch 10 itself cut-offs control
Circuit is overall to be cut-off, and may finally be realized according to the intermittent of the intermittent pulse control signal control charge-discharge circuit cut-off
Break-make.As shown in figure 4, corresponding device of the present invention is compared with the electrolyte utilization rate of conventional apparatus, it is electric in low flow rate β
Solution liquid utilization rate is greatly enhanced.
Based on the device, improving the method for electrolyte utilization rate is：One is being inputted to pulsed timed power switch 10
The intermittent pulse signal cut-off, makes charge-discharge system no longer constantly charge to the electrolyte in flow battery, but
It is transformed to intermittent charging.In the period do not charged, the still continuous service of circulating pump 6, ensures in pile and fluid reservoir
Electrolyte fully mix, to reduce the difference of electrolyte state-of-charge (SoC) between battery pile and fluid reservoir, until reach
Charge cutoff voltage, completes charging process and enters discharge process.In discharge process, also make between pulsed timed power switch 10
The formula of having a rest is cut-off, and keeps the intermittent electric discharge of electrolyte, until reaching discharge cut-off voltage, completes discharge process.Thus one is formed
Charge and discharge cycles.
The specific method for improving electrolyte utilization rate is described below in detail, step is as follows：
Isometric electrolyte is added in anode electrolyte fluid reservoir 5 and electrolyte liquid fluid reservoir 7 first, and at two
A magnet rotor 8 is separately added into fluid reservoir, ensures the uniformity that electrolyte mixes in system operation.Open the circulation pump 6,
Positive and negative anodes electrolyte is flowed in infusion pipeline 4, respectively by pile end plate 1, pile PP plates 2, anode electrolyte into
Liquid mouth 13, electrolyte liquid inlet 17 enter in the single-cell structure unit 3 in pile, and redox occurs in monocell
Reaction, state-of-charge (SoC) increase of electrolyte after the completion of reaction, then pass through anode electrolyte liquid outlet 12 and negative electricity respectively
Solution liquid liquid outlet 16 is returned in anode electrolyte fluid reservoir 5 and electrolyte liquid fluid reservoir 7.According to the volume of positive and negative anodes electrolyte
The charging and discharging time of theory is calculated, the theory charging and discharging time is divided into some time input computer 11
(being preferably divided into 5-20 sections), the state of control pulsed timed power switch 10, exports battery charging and discharging detection device with this
The electric current of pulsed, i.e.,：Beginning-charging-shutdown-charging-shutdown ... electric discharge-shutdown-electric discharge-shutdown-end, downtime
Do not limit (being preferably 1min so as to making subject to electrolyte fully mixes).When pulsed timed power switch 10 connects, electricity
Pond charge and discharge electric detection means 9 starts, to 14 output current of collector, to make system charge by predetermined pulse formula charge and discharge system.
And in stopping process, two 6 continuous runnings of circulating pump, reduce electrolyte state-of-charge between battery pile and fluid reservoir
(SoC) difference, reduces the concentration polarization between pile and fluid reservoir.Closure connects subsequent pulsed timed power switch 10 again
Logical, system continues charging process.Above-mentioned pulse process reciprocation cycle n times, when the collector plate 14 of external charge-discharge system is adopted
Integrate (preferably, charge cutoff voltage is set as 1.7V) when the voltage of battery has reached charge cutoff voltage, charging is tied
Beam, starts discharge process.System with still keeping pulsed discharge process at this time, until the collector plate 14 of external charge-discharge system
(preferably, it be 0.8V to set discharge cut-off voltage) when the voltage of battery has reached discharge cut-off voltage is collected, is discharged
Process terminates, and completes a complete charge and discharge cycles.
Embodiment described above is a kind of preferable scheme of the present invention, and so it is not intended to limiting the invention.Have
The those of ordinary skill of technical field is closed, without departing from the spirit and scope of the present invention, various changes can also be made
Change and modification.For example, the concrete structure of flow battery can use various modes of the prior art, embodiment is not limited to
Described in structure.Therefore the technical solution that all modes for taking equivalent substitution or equivalent transformation are obtained, all falls within the present invention
Protection domain in.
Claims (9)
- A kind of 1. flow battery pulsed charge-discharge system for improving electrolyte utilization rate, it is characterised in that flow battery both sides Pile end plate (1) on have anode electrolyte inlet (13), electrolyte liquid inlet (17), anode electrolyte liquid outlet (12) and electrolyte liquid liquid outlet (16), anode electrolyte inlet (13) and anode electrolyte liquid outlet (12) are by defeated Liquid pipeline connection anode electrolyte fluid reservoir (5), forms the circulation loop of anode electrolyte；Electrolyte liquid inlet (17) and Electrolyte liquid liquid outlet (16) connects electrolyte liquid fluid reservoir (7) by infusion pipeline, forms following for electrolyte liquid Loop back path；The circulating pump (6) for providing electrolyte conveying power is both provided with the infusion pipeline；Anode electrolyte stores up Agitating device is equipped with flow container (5) and electrolyte liquid fluid reservoir (7)；The external discharge and recharge system of collector plate (14) of flow battery System, charge-discharge system include battery charging and discharging detection device (9) and pulsed timed power switch (10), pulsed Timing power supply Switch (10) is series in the charge-discharge circuit of battery charging and discharging detection device and collector plate (14), for controlling charge-discharge circuit Intermittent break-make.
- 2. the flow battery pulsed charge-discharge system of electrolyte utilization rate is improved as claimed in claim 1, it is characterised in that The pulsed timed power switch (10) is connected with the computer (11) for input pulse control signal.
- 3. the flow battery pulsed charge-discharge system of electrolyte utilization rate is improved as claimed in claim 1, it is characterised in that The agitating device is magnet rotor (8).
- 4. the flow battery pulsed charge-discharge system of electrolyte utilization rate is improved as claimed in claim 1, it is characterised in that The electric pile structure of flow battery is：Some single-cell structure units (3) are clamped between both sides PP plates (2), are divided outside the PP plates of both sides Pile end plate (1) is not fixed with.
- 5. the flow battery pulsed charge-discharge system of electrolyte utilization rate is improved as claimed in claim 1, it is characterised in that The flow battery is all-vanadium flow battery, zinc-bromine flow battery or Zn-Ni liquid battery.
- A kind of 6. method that electrolyte utilization rate is improved using system as claimed in claim 2, it is characterised in that step is as follows： Isometric electrolyte is added in anode electrolyte fluid reservoir (5) and electrolyte liquid fluid reservoir (7) first, and in two liquid storages Agitating device is separately turned in tank to mix the electrolyte in tank；Open the circulation pump (6), makes positive and negative anodes electrolyte in infusion pipeline (4) flowing, passes through pile end plate (1), pile PP plates (2), anode electrolyte inlet (13), electrolyte liquid feed liquor respectively in Mouth (17) enters in the single-cell structure unit (3) in pile, and redox reaction occurs in monocell, makes the lotus of electrolyte Electricity condition increase, then respectively anode electrolyte is returned to by anode electrolyte liquid outlet (12) and electrolyte liquid liquid outlet (16) In fluid reservoir (5) and electrolyte liquid fluid reservoir (7), circulation loop is formed；Calculated according to the volume of positive and negative anodes electrolyte Theoretical charging interval and theoretical discharge time, will be divided into some time input computer (11), control the charging and discharging time Pulsed timed power switch (10) cut-offs state, makes the electric current of battery charging and discharging detection device output pulsed, electrolyte Intermittent charging is obtained in pile；The period that charge and discharge electric detection means does not charge within the pulse period, driving positive and negative anodes electricity The circulating pump (6) of solution liquid circulation still keeps operating；When the collector plate (14) of external charge-discharge system collects the voltage of battery When having reached charge cutoff voltage, charging terminates, and starts discharge process, and system was discharged with still keeping pulsed at this time Journey, when voltage that the collector plate (14) of external charge-discharge system collects battery has reached discharge cut-off voltage, electric discharge Process terminates, and completes a complete charge and discharge cycles.
- 7. method as claimed in claim 6, it is characterised in that in each pulse period of charge or discharge, when amounting to charging Between be not less than the theoretical charging interval, amounting to discharge time is not less than the theoretical discharge time.
- 8. method as claimed in claim 6, it is characterised in that charge cutoff voltage is arranged to 1.7V.
- 9. method as claimed in claim 6, it is characterised in that discharge cut-off voltage is arranged to 0.8V.
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