CN105702997A - Redox flow battery rebalance system, refox flow battery system and method for cycle capacity rebalance of redox flow battery - Google Patents
Redox flow battery rebalance system, refox flow battery system and method for cycle capacity rebalance of redox flow battery Download PDFInfo
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- CN105702997A CN105702997A CN201610221278.0A CN201610221278A CN105702997A CN 105702997 A CN105702997 A CN 105702997A CN 201610221278 A CN201610221278 A CN 201610221278A CN 105702997 A CN105702997 A CN 105702997A
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- 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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Abstract
The invention provides a redox flow battery rebalance system, a redox flow battery system containing the same and a method for cycle capacity rebalance of a redox flow battery. The above system or method is particularly and suitably used for a Fe-Cr flow battery. The redox flow battery rebalance system has a flow battery structure, wherein a positive electrolyte storage tank of the rebalance system is used for storing a positive electrode containing active positive ions, a negative electrolyte storage tank of the rebalance system is simultaneously taken as a positive electrode storage tank of a working flow battery and is used for storing a positive electrolyte of the working flow battery, and the redox flow battery rebalance system is only used for charging after being started. With the technical scheme provided by the invention, the redox flow battery rebalance system has the advantages of high rebalance efficiency and convenience, rapidness and high efficiency in operation.
Description
Technical field
The invention belongs to field of electrochemical batteries, particularly relate to a kind of flow battery rebalancing system, a kind of flow battery system comprising described flow battery rebalancing system, and a kind of method of flow battery circulation volume reequilibrate。
Background technology
Electrochemistry flow battery (electrochemicalflowcell), is a kind of novel bulk electrochemical energy storage device referred to as flow battery (flowredoxcell or redoxflowcell)。Flow battery is applicable to extensive energy storage, is a kind of energy conversion device, by electrical power storage in electrolyte solution, the energy of storage can be converted into electric energy and discharge during electric discharge during charging。The output of battery depends on the size and number of battery pile, and storage volume then depends on concentration and the storage capacity of electrolyte。In battery charge and discharge process, only the ionic valence condition in both positive and negative polarity electrolyte changes, fast response time, can deep discharge, have extended cycle life, the renewable recycling of electrolyte, run safety, pollution-free, simple to operate, maintain easily。
Ferrum-chromium system flow battery, is also known as Fe-Cr flow battery, is the one of flow battery。During the charging of described Fe-Cr flow battery, the Fe in positive pole tank2+It is input on anode by pump and is converted into Fe3+, meanwhile, the Cr in cathode pot3+It is input in battery cathode and is converted into Cr2+, internal current then completes the conduction of positive and negative interpolar conductive carrier by ion exchange membrane；High-octane electrolyte solution after conversion is cycled back in respective storage tank and stores。And discharge process is contrary with above-mentioned charging process。
Ferrum, chromium ion are conduction memory carriers in Fe-Cr flow battery system, and its concentration in the solution and practical efficiency decide the charging and discharging capabilities of battery system。Due to the permeability of ion exchange membrane, both positive and negative polarity ferrum, chromium ion constantly migrate with hydrone, the generation of simultaneous side reaction, and Fe-Cr flow battery system is after experiencing long-time discharge and recharge, it may appear that positive pole Fe2+, negative pole Cr3+Concentration serious unbalance, positive-active cation Fe2+Concentration reduces, and unnecessary Fe occurs3+, this will cause that battery discharge capacity decays, thus having a strong impact on the serviceability of battery。
Therefore, both positive and negative polarity electrolyte active ion concentration balance is made to be improve electrolyte utilization rate and recover the main path of battery performance by certain methods。All-vanadium flow battery (VanadiumRedoxFlowBattery, VRB) is a kind of active substance is the redox cell circulating liquid, falls within the one of flow battery。In the prior art, the effect of capacity restoration is reached often through interpolation organic molecule in the electrolyte of all-vanadium flow battery。Additionally, early stage, in the Fe-Cr flow battery system research of NASA (NASA), adopts Fe3+-H2Rebalance cell, but its hydrogen electeode need to use Pt or W catalyst, and Pt is penetrated in electrolyte liquid by ionic membrane, makes negative pole generation evolving hydrogen reaction；But, Pt is costly；Further, W poor catalyst stability, use a period of time, arise that deactivation phenomenom。As can be seen here, electrolyte all can be produced certain pollution by these methods of the prior art, causes the generation of side reaction, and causes that reequilibrate performance is gradually reduced。
Therefore, design and develop a kind of flow battery efficiently and conveniently realizing circulation volume reequilibrate, be one of emphasis of paying close attention to of current this area research staff。
Summary of the invention
In view of the many disadvantages that flow battery of the prior art exists in realizing circulation volume reequilibrate, it is intended to there is efficient recovery battery capacity, extend battery, ensure the serviceability of battery, a first aspect of the present invention provides a kind of flow battery rebalancing system, for the reequilibrate of the circulation volume for the treatment of fluid flow battery；Described flow battery rebalancing system has the structure of flow battery, including: rebalancing system anolyte liquid storage tank, rebalancing system cathode electrolyte storage tank, positive pole circulating pump, negative pole circulating pump, circulation line and valve, power supply, rebalance cell heap and circuit thereof；Wherein, described rebalance cell heap includes: positive pole, negative pole and ionic membrane；
Wherein, described rebalancing system anolyte liquid storage tank is connected with described positive pole by positive pole circulation line, and positive pole circulating pump is for circulation conveying anode electrolyte between described rebalancing system anolyte liquid storage tank and described positive pole；Described rebalancing system cathode electrolyte storage tank is connected with described negative pole by negative pole circulation line, and negative pole circulating pump is for circulation conveying electrolyte liquid between described rebalancing system cathode electrolyte storage tank and described negative pole；
Wherein, described rebalancing system anolyte liquid storage tank is for storing the anode electrolyte containing active cation；Described rebalancing system cathode electrolyte storage tank is simultaneously as the positive pole storage tank of described treatment fluid flow battery, for storing the anode electrolyte of described treatment fluid flow battery；Wherein, described flow battery rebalancing system is only charged after starting。
In above-described flow battery rebalancing system, described " treatment fluid flow battery " refers to the flow battery for discharge and recharge when work runs, the positive pole storage tank of this treatment fluid flow battery and described rebalancing system cathode electrolyte storage tank, in like manner it can be seen that the electrolyte liquid of described rebalancing system itself is the anode electrolyte of described treatment fluid flow battery。Additionally, what deserves to be explained is, " flow battery " described in this specification is not the flow battery of any type of specific finger, and it can be Fe-Cr flow battery, all-vanadium flow battery etc.。
In above-described flow battery rebalancing system, described flow battery rebalancing system has the structure of flow battery, refer to that this flow battery rebalancing system substantially also uses the basic structure of flow battery, primary difference is that the positive pole storage tank for the treatment of fluid flow battery and described rebalancing system cathode electrolyte storage tank, and this flow battery rebalancing system is designed to be merely able to be charged, and can not discharge。
A second aspect of the present invention, provide a kind of Fe-Cr flow battery rebalancing system, for the reequilibrate of the circulation volume of Fe-Cr flow battery, described Fe-Cr flow battery rebalancing system has the structure of flow battery, including: rebalancing system anolyte liquid storage tank, rebalancing system cathode electrolyte storage tank, positive pole circulating pump, negative pole circulating pump, circulation line and valve, power supply, rebalance cell heap and circuit thereof；Wherein, described rebalance cell heap includes: positive pole, negative pole and ionic membrane；
Wherein, described rebalancing system anolyte liquid storage tank is connected with described positive pole by positive pole circulation line, and described rebalancing system anolyte liquid storage tank is for storing the Fe as anode electrolyte2+Initial concentration electrolyte, it can be delivered to described positive pole by positive pole circulating pump, is then return in described rebalancing system anolyte liquid storage tank；Described rebalancing system cathode electrolyte storage tank is connected with described negative pole by negative pole circulation line, described rebalancing system cathode electrolyte storage tank is simultaneously as the positive pole storage tank of described Fe-Cr flow battery, for storing the anode electrolyte of described Fe-Cr flow battery；Negative pole circulating pump, for the anode electrolyte of described Fe-Cr flow battery is delivered to described negative pole, is then return in described rebalancing system cathode electrolyte storage tank；
Wherein, described Fe-Cr flow battery rebalancing system is only charged after starting。
Fe in the Fe-Cr flow battery rebalancing system described in a second aspect of the present invention, in described rebalancing system anolyte liquid storage tank2+Initial concentration electrolyte, after this system runs a period of time, also can be gradually consumed, Fe therein2+Concentration can be gradually lowered；When concentration is extremely low, then need to change described rebalancing system anode electrolyte。
A third aspect of the present invention, it is provided that a kind of flow battery system, it includes treatment fluid flow battery and flow battery rebalancing system described according to a first aspect of the present invention；After the charge and discharge cycles capacity monitoring described treatment fluid flow battery is substantially decayed, start described flow battery rebalancing system and be charged, continuous service until described treatment fluid flow battery anode electrolyte in active cation concentration recover；Active cation concentration in the anode electrolyte of described treatment fluid flow battery closes described flow battery rebalancing system after recovering。Wherein, described " substantially decay " refers to that charge and discharge cycles capacity attenuation to a certain predetermined value or occurs that the research staff such as violent decay regard as the situation of substantially decay。Visible, in described treatment fluid flow battery last normal course of operation incessantly, described flow battery rebalancing system can on-line operation, it is achieved the recovery of charge/discharge capacity。
A fourth aspect of the present invention, it is provided that a kind of Fe-Cr flow battery system, it includes Fe-Cr flow battery and Fe-Cr flow battery rebalancing system described according to a second aspect of the present invention；After the charge and discharge cycles capacity monitoring described Fe-Cr flow battery is substantially decayed, start described Fe-Cr flow battery rebalancing system and be charged, continuous service until described Fe-Cr flow battery anode electrolyte in Fe2+Concentration is recovered；Fe in the anode electrolyte of described Fe-Cr flow battery2+Concentration closes described Fe-Cr flow battery rebalancing system after recovering。Similarly, wherein, described " substantially decay " refers to that charge and discharge cycles capacity attenuation to a certain predetermined value or occurs that the research staff such as violent decay regard as the situation of substantially decay。Visible, in described Fe-Cr flow battery continuously and uninterruptedly normal course of operation, described Fe-Cr flow battery rebalancing system can on-line operation, it is achieved the recovery of charge/discharge capacity。
In this Fe-Cr flow battery system, for charging process (discharge process is contrary), the operation principle of described Fe-Cr flow battery is expressed as follows by ionic equation:
Positive pole: Fe2+-e-→Fe3+(charging)
Negative pole: Cr3++e-→Cr2+(charging)。
In this Fe-Cr flow battery system, the operation principle of described Fe-Cr flow battery rebalancing system is expressed as follows by ionic equation:
Positive pole Fe2+-e-→Fe3+(charging)
Negative pole Fe3++e-→Fe2+(charging)。
As can be seen here, by applying constant current to described Fe-Cr flow battery rebalancing system, and control supply voltage, the generation of other reactions can be suppressed；In this course of reaction, the negative pole of this system can reduce gradually Fe-Cr flow battery positive pole storage tank in accumulation irreversible Fe3+Ion, thus reaching to recover the positive pole Fe of Fe-Cr flow battery2+Ion concentration and negative pole Cr3+Ion concentration balance purpose。
Based on any of the above system, a fifth aspect of the present invention, it is provided that a kind of method of flow battery circulation volume reequilibrate, the process employs the flow battery system described in third aspect present invention, and specifically include following steps:
(1) after the charge and discharge cycles capacity monitoring described treatment fluid flow battery is substantially decayed, start described flow battery rebalancing system immediately to be charged: connect described power supply, and by the valve opening on described positive pole circulation line, by described positive pole circulating pump, anode electrolyte is delivered to described positive pole from described rebalancing system anolyte liquid storage tank, cation in described anode electrolyte, after positive pole completes betatopic, is back to described rebalancing system anolyte liquid storage tank；Simultaneously by the valve opening on described negative pole circulation line, by described negative pole circulating pump, electrolyte liquid is delivered to described negative pole from described rebalancing system cathode electrolyte storage tank, cation in described electrolyte liquid negative pole complete after electronics, be back to described rebalancing system cathode electrolyte storage tank；
(2) it is performed continuously over charging until the active cation concentration in the anode electrolyte of described treatment fluid flow battery is recovered；Active cation concentration in the anode electrolyte of described treatment fluid flow battery closes described flow battery rebalancing system after recovering；
(3) step (1)～(2) are repeated, until when the active cation concentration in the anode electrolyte detected in described rebalancing system anolyte liquid storage tank is low to moderate default replacing value, change this anode electrolyte, be then carried out step (1)。
Preferably, in the above-mentioned methods, described valve is butterfly valve or ball valve。
Preferably, in the above-mentioned methods, described flow battery system adopts PLC to control。
A sixth aspect of the present invention, it is provided that a kind of method of Fe-Cr flow battery circulation volume reequilibrate, the process employs the Fe-Cr flow battery system described in fourth aspect present invention, and specifically includes following steps:
(1) after the charge and discharge cycles capacity monitoring described Fe-Cr flow battery is substantially decayed, start described Fe-Cr flow battery rebalancing system immediately to be charged: connect described power supply, and by the valve opening on described positive pole circulation line, by described positive pole circulating pump, anode electrolyte is delivered to described positive pole, the Fe in described anode electrolyte from described rebalancing system anolyte liquid storage tank2+After positive pole completes betatopic, it is back to described rebalancing system anolyte liquid storage tank；Simultaneously by the valve opening on described negative pole circulation line, by described negative pole circulating pump, electrolyte liquid is delivered to described negative pole, the Fe in described electrolyte liquid from described rebalancing system cathode electrolyte storage tank3+Negative pole complete after electronics, be back to described rebalancing system cathode electrolyte storage tank；
(2) be performed continuously over charging until described Fe-Cr flow battery anode electrolyte in Fe2+Concentration is recovered；Fe in the anode electrolyte of described Fe-Cr flow battery2+Concentration closes described Fe-Cr flow battery rebalancing system after recovering；
(3) step (1)～(2) are repeated, until the Fe in the anode electrolyte detected in the anolyte liquid storage tank of described Fe-Cr flow battery rebalancing system2+When concentration is low to moderate default replacing value, change this anode electrolyte, be then carried out step (1)。
Preferably, in the above-mentioned methods, described valve is butterfly valve or ball valve。
Preferably, in the above-mentioned methods, described Fe-Cr flow battery system adopts PLC to control。
The present invention passes through flow battery rebalancing system, improves electrolyte utilization rate, ensures that flow battery system long-term stability is powered, extends battery；Further, in this flow battery rebalancing system running, produce without other noxious substances or impurity。
Technical scheme provided by the present invention, reequilibrate efficiency is high, by change the mode of described flow battery rebalancing system anode electrolyte just can quick-recovery reequilibrate ability soon, therefore, simple to operate, convenient, efficient。
Technical scheme provided by the present invention is particularly well-suited to Fe-Cr flow battery。In the Fe-Cr flow battery system comprising Fe-Cr flow battery and Fe-Cr flow battery rebalancing system, Fe-Cr flow battery rebalancing system is by unnecessary in anode electrolyte and irreversible Fe3+It is reduced to active cation Fe2+, so that positive pole Fe2+, negative pole Cr3+Ion concentration balances, and reaches the purpose of recovery system charge/discharge capacity。The method is simple to operate, and reequilibrate process is without introducing other additives, without generating poisonous or electrolyte producing the material polluted and fast response time；Therefore, system provided by the present invention, method are respectively provided with good application prospect and market potential。
Accompanying drawing explanation
Fig. 1 is the schematic appearance of flow battery system described according to one embodiment of present invention, and this flow battery system includes treatment fluid flow battery and flow battery rebalancing system；
Fig. 2 is the operation logic schematic diagram of Fe-Cr flow battery system described according to one embodiment of present invention, and this Fe-Cr flow battery system includes Fe-Cr flow battery and Fe-Cr flow battery rebalancing system；
Wherein, A represents Fe-Cr flow battery rebalancing system；B represents Fe-Cr flow battery；1 represents rebalancing system anolyte liquid storage tank；2,4,6,7,9,10,13,15 represent valve；3,5,11,12 represent circulating pump；8 represent rebalancing system cathode electrolyte storage tank (being also simultaneously the positive pole storage tank of Fe-Cr flow battery)；The 14 negative pole storage tanks representing Fe-Cr flow battery；
Fig. 3 is that the Fe-Cr flow battery in Fe-Cr flow battery system described according to one embodiment of present invention is after 100 charge and discharge cycles, open Fe-Cr flow battery rebalancing system, the relative capacity relation curve with period that discharges of this Fe-Cr flow battery；
Fig. 4 is the coulombic efficiency in an embodiment according to Fe-Cr flow battery system of the present invention, energy efficiency, voltage efficiency change curve。
Detailed description of the invention
A first aspect of the present invention, it is provided that a kind of flow battery rebalancing system, for the reequilibrate of the circulation volume for the treatment of fluid flow battery；Described flow battery rebalancing system has the structure of flow battery, including: rebalancing system anolyte liquid storage tank, rebalancing system cathode electrolyte storage tank, positive pole circulating pump, negative pole circulating pump, circulation line and valve, power supply, rebalance cell heap and circuit thereof；Wherein, described rebalance cell heap includes: positive pole, negative pole and ionic membrane；
Wherein, described rebalancing system anolyte liquid storage tank is connected with described positive pole by positive pole circulation line, and positive pole circulating pump is for circulation conveying anode electrolyte between described rebalancing system anolyte liquid storage tank and described positive pole；Described rebalancing system cathode electrolyte storage tank is connected with described negative pole by negative pole circulation line, and negative pole circulating pump is for circulation conveying electrolyte liquid between described rebalancing system cathode electrolyte storage tank and described negative pole；
Wherein, described rebalancing system anolyte liquid storage tank is for storing the anode electrolyte containing active cation；Described rebalancing system cathode electrolyte storage tank is simultaneously as the positive pole storage tank of described treatment fluid flow battery, for storing the anode electrolyte of described treatment fluid flow battery；Wherein, described flow battery rebalancing system is only charged after starting。
A second aspect of the present invention, provide a kind of Fe-Cr flow battery rebalancing system, for the reequilibrate of the circulation volume of Fe-Cr flow battery, described Fe-Cr flow battery rebalancing system has the structure of flow battery, including: rebalancing system anolyte liquid storage tank, rebalancing system cathode electrolyte storage tank, positive pole circulating pump, negative pole circulating pump, circulation line and valve, power supply, rebalance cell heap and circuit thereof；Wherein, described rebalance cell heap includes: positive pole, negative pole and ionic membrane；
Wherein, described rebalancing system anolyte liquid storage tank is connected with described positive pole by positive pole circulation line, and described rebalancing system anolyte liquid storage tank is for storing the Fe as anode electrolyte2+Initial concentration electrolyte, it can be delivered to described positive pole by positive pole circulating pump, is then return in described rebalancing system anolyte liquid storage tank；Described rebalancing system cathode electrolyte storage tank is connected with described negative pole by negative pole circulation line, described rebalancing system cathode electrolyte storage tank is simultaneously as the positive pole storage tank of described Fe-Cr flow battery, for storing the anode electrolyte of described Fe-Cr flow battery；Negative pole circulating pump, for the anode electrolyte of described Fe-Cr flow battery is delivered to described negative pole, is then return in described rebalancing system cathode electrolyte storage tank；
Wherein, described Fe-Cr flow battery rebalancing system is only charged after starting。
A third aspect of the present invention, it is provided that a kind of flow battery system, it includes treatment fluid flow battery and flow battery rebalancing system described according to a first aspect of the present invention；After the charge and discharge cycles capacity monitoring described treatment fluid flow battery is substantially decayed, start described flow battery rebalancing system and be charged, continuous service until described treatment fluid flow battery anode electrolyte in active cation concentration recover；Active cation concentration in the anode electrolyte of described treatment fluid flow battery closes described flow battery rebalancing system after recovering。
A fourth aspect of the present invention, it is provided that a kind of Fe-Cr flow battery system, it includes Fe-Cr flow battery and Fe-Cr flow battery rebalancing system described according to a second aspect of the present invention；After the charge and discharge cycles capacity monitoring described Fe-Cr flow battery is substantially decayed, start described Fe-Cr flow battery rebalancing system and be charged, continuous service until described Fe-Cr flow battery anode electrolyte in Fe2+Concentration is recovered；Fe in the anode electrolyte of described Fe-Cr flow battery2+Concentration closes described Fe-Cr flow battery rebalancing system after recovering。
A fifth aspect of the present invention, it is provided that a kind of method of flow battery circulation volume reequilibrate, described method adopts flow battery system described according to a third aspect of the present invention, and comprises the following steps:
(1) after the charge and discharge cycles capacity monitoring described treatment fluid flow battery is substantially decayed, start described flow battery rebalancing system immediately to be charged: connect described power supply, and by the valve opening on described positive pole circulation line, by described positive pole circulating pump, anode electrolyte is delivered to described positive pole from described rebalancing system anolyte liquid storage tank, cation in described anode electrolyte, after positive pole completes betatopic, is back to described rebalancing system anolyte liquid storage tank；Simultaneously by the valve opening on described negative pole circulation line, by described negative pole circulating pump, electrolyte liquid is delivered to described negative pole from described rebalancing system cathode electrolyte storage tank, cation in described electrolyte liquid negative pole complete after electronics, be back to described rebalancing system cathode electrolyte storage tank；
(2) it is performed continuously over charging until the active cation concentration in the anode electrolyte of described treatment fluid flow battery is recovered；Active cation concentration in the anode electrolyte of described treatment fluid flow battery closes described flow battery rebalancing system after recovering；
(3) step (1)～(2) are repeated, until when the active cation concentration in the anode electrolyte detected in described rebalancing system anolyte liquid storage tank is low to moderate default replacing value, change this anode electrolyte, be then carried out step (1)。
In a preferred embodiment, described valve is butterfly valve or ball valve。
In a preferred embodiment, described flow battery system adopts PLC to control。
A sixth aspect of the present invention, it is provided that a kind of method of Fe-Cr flow battery circulation volume reequilibrate, described method adopts Fe-Cr flow battery system described according to a fourth aspect of the present invention, and comprises the following steps:
(1) after the charge and discharge cycles capacity monitoring described Fe-Cr flow battery is substantially decayed, start described Fe-Cr flow battery rebalancing system immediately to be charged: connect described power supply, and by the valve opening on described positive pole circulation line, by described positive pole circulating pump, anode electrolyte is delivered to described positive pole, the Fe in described anode electrolyte from described rebalancing system anolyte liquid storage tank2+After positive pole completes betatopic, it is back to described rebalancing system anolyte liquid storage tank；Simultaneously by the valve opening on described negative pole circulation line, by described negative pole circulating pump, electrolyte liquid is delivered to described negative pole, the Fe in described electrolyte liquid from described rebalancing system cathode electrolyte storage tank3+Negative pole complete after electronics, be back to described rebalancing system cathode electrolyte storage tank；
(2) be performed continuously over charging until described Fe-Cr flow battery anode electrolyte in Fe2+Concentration is recovered；Fe in the anode electrolyte of described Fe-Cr flow battery2+Concentration closes described Fe-Cr flow battery rebalancing system after recovering；
(3) step (1)～(2) are repeated, until the Fe in the anode electrolyte detected in the anolyte liquid storage tank of described Fe-Cr flow battery rebalancing system2+When concentration is low to moderate default replacing value, change this anode electrolyte, be then carried out step (1)。
In a preferred embodiment, described valve is butterfly valve or ball valve。
In a preferred embodiment, described Fe-Cr flow battery system adopts PLC to control。
Embodiment 1
As in figure 2 it is shown, a kind of Fe-Cr flow battery system, include Fe-Cr flow battery B and Fe-Cr flow battery rebalancing system A the two major part。Wherein, the power of this Fe-Cr flow battery B is 1kW and includes:
The battery pile being made up of positive pole, negative pole and ionic membrane, this battery pile charging circuit is connected to charge power supply；This Fe-Cr flow battery B discharge circuit is equipped with load；
Positive pole storage tank 8, by be provided with valve 7 with 9 positive pole circulation line be connected with positive pole；This positive pole storage tank 8 is used for storing mainly containing Fe2+Anode electrolyte；Described anode electrolyte can be delivered to positive pole by positive pole circulating pump 11, reacts, and is then return in this positive pole storage tank 8；
Negative pole storage tank 14, by be provided with valve 13 with 15 negative pole circulation line be connected with negative pole；This negative pole storage tank 14 is used for storing mainly containing Cr3+Electrolyte liquid；Described electrolyte liquid can be delivered to negative pole by negative pole circulating pump 12, reacts, and is then return in this negative pole storage tank 14；
The charging process of this Fe-Cr flow battery B is: Open valve 7 and 9, and anode electrolyte carried by positive pole circulating pump 11, and makes anode electrolyte circulate between positive pole storage tank 8 and positive pole；Meanwhile, Open valve 13 and 15, electrolyte liquid carried by negative pole circulating pump 12, and makes electrolyte liquid circulate between negative pole storage tank 14 and negative pole；Connect charge power supply；Continuous service said process so that this Fe-Cr flow battery B completes charging。
The discharge process of this Fe-Cr flow battery B is similar with above-mentioned charging process, and operation principle is contrary, differs primarily in that disconnection charge power supply and passes through discharge circuit by power transmission to described load。
Described Fe-Cr flow battery rebalancing system A includes:
The rebalance cell heap being made up of positive pole, negative pole and ionic membrane, this rebalance cell heap charging circuit is connected to charge power supply；
Rebalancing system anolyte liquid storage tank 1, by be provided with valve 2 with 4 positive pole circulation line be connected with positive pole；This rebalancing system anolyte liquid storage tank 1 is for storing the Fe as anode electrolyte2+Initial electrolysis liquid；This Fe2+Initial electrolysis liquid can be delivered to positive pole by positive pole circulating pump 3, reacts, and is then return in this rebalancing system anolyte liquid storage tank 1；
Rebalancing system cathode electrolyte storage tank 8 (i.e. above-mentioned positive pole storage tank 8), by be provided with valve 6 with 10 negative pole circulation line be connected with negative pole；This rebalancing system cathode electrolyte storage tank 8 (i.e. above-mentioned positive pole storage tank 8) is main containing Fe for what store in above-mentioned Fe-Cr flow battery B2+Anode electrolyte, in this rebalancing system A, it is considered electrolyte liquid；Described electrolyte liquid can be delivered to negative pole by negative pole circulating pump 5, reacts, and is then return in this rebalancing system cathode electrolyte storage tank 8 (i.e. above-mentioned positive pole storage tank 8)。
After the Fe-Cr flow battery B discharge and recharge 100 times of this 1kW, monitor its circulation volume and substantially decay, positive-active cation Fe occur2+Concentration reduces, and unnecessary Fe occurs3+, then start described Fe-Cr flow battery rebalancing system A immediately, connect charging current 20A, the charge power supply of charge cutoff voltage 2V is charged:
As in figure 2 it is shown, Open valve 2,4,6,10, and start positive pole circulating pump 3 and negative pole circulating pump 5；Negative pole circulating pump 5 makes the Fe of the great quantities of spare in this rebalancing system cathode electrolyte storage tank 83+Along with Fe2+It is pumped to the negative pole of rebalance cell heap, and makes unnecessary Fe3+It is reduced into Fe2+, it is back in this rebalancing system cathode electrolyte storage tank 8；Meanwhile, positive pole circulating pump 3 makes the anode electrolyte in this rebalancing system anolyte liquid storage tank 1 be pumped to the positive pole of rebalance cell heap, part Fe therein2+It is oxidized to Fe3+, then it is back in this rebalancing system anolyte liquid storage tank 1；In above process, Fe-Cr flow battery B is continued for properly functioning incessantly；
It is performed continuously over charging process until Fe in the anode electrolyte of Fe-Cr flow battery B2+Concentration is recovered；Fe in the anode electrolyte of described Fe-Cr flow battery B2+Concentration closes described Fe-Cr flow battery rebalancing system A after recovering。In above process, Fe-Cr flow battery B is continued for properly functioning incessantly, in other words, and the recovery of charge/discharge capacity of described Fe-Cr flow battery rebalancing system A canbe used on line。Wherein, the opening time of described Fe-Cr flow battery rebalancing system A, can calculate according to capacity attenuation。
Fe-Cr flow battery B carried out in the process of reequilibrate at Fe-Cr flow battery rebalancing system A utilized above, the Fe in the anode electrolyte of Fe-Cr flow battery rebalancing system A2+It is constantly consume。Therefore, as the Fe in the anode electrolyte in the anolyte liquid storage tank 1 described Fe-Cr flow battery rebalancing system A being detected2+When concentration is low to moderate default replacing value, online or off-line changes this anode electrolyte；After replacing, Fe-Cr flow battery rebalancing system A can give full play to again reequilibrate effect described above, thus the continuous service of Fe-Cr flow battery B can be maintained。And the capacity of this anolyte liquid storage tank 1 can be designed according to battery B capacity attenuation speed and operation time。
In addition, as shown in Figure 3, the relation curve of electric discharge relative capacity and period that it is the Fe-Cr flow battery B described in the present embodiment 1, and this Fe-Cr flow battery is as shown in table 1 below in the battery capacity opened before and after Fe-Cr flow battery rebalancing system A and efficiency change:
| Capacity (AH) | Current efficiency (%) | Energy efficiency (%) | Voltage efficiency (%) | |
| Initially | 1300-1400 | 91-94 | 80-83 | 86-88 |
| After 100 circulations | 930-980 | 91-94 | 80-83 | 86-88 |
| After reequilibrate is opened | 1170-1400 | 91-94 | 80-83 | 86-88 |
Table 1
Obviously, the Fe-Cr flow battery B of 1kW there occurs capacity attenuation, and after opening Fe-Cr flow battery rebalancing system A, the experimental data of table 1 shows that the charge/discharge capacity of Fe-Cr flow battery B recovers to initial capacity state, and the every efficiency of system keeps normal。
Further, as shown in Figure 4, after Fe-Cr flow battery B carries out 100 charge and discharge cycles, Fe-Cr flow battery rebalancing system A is opened；Afterwards, the coulombic efficiency of this Fe-Cr flow battery B, energy efficiency, voltage efficiency are all gradually brought to original state, and remain stable for。
As can be seen here, after opening Fe-Cr flow battery rebalancing system A, the active Fe in the positive pole storage tank 8 of Fe-Cr flow battery B2+Concentration obtains and effectively maintains, it is achieved that the reequilibrate of its circulation volume。
Above specific embodiments of the invention being described in detail, but it is intended only as example, the present invention is not restricted to particular embodiments described above。To those skilled in the art, any equivalent modifications that the present invention is carried out and replacement are also all among scope of the invention。Therefore, the equalization made without departing from the spirit and scope of the invention converts and amendment, all should contain within the scope of the invention。
Claims (10)
1. a flow battery rebalancing system, for the reequilibrate of the circulation volume for the treatment of fluid flow battery；Described flow battery rebalancing system has the structure of flow battery, including: rebalancing system anolyte liquid storage tank, rebalancing system cathode electrolyte storage tank, positive pole circulating pump, negative pole circulating pump, circulation line and valve, power supply, rebalance cell heap and circuit thereof；Wherein, described rebalance cell heap includes: positive pole, negative pole and ionic membrane；
It is characterized in that: described rebalancing system anolyte liquid storage tank is connected with described positive pole by positive pole circulation line, positive pole circulating pump is for circulation conveying anode electrolyte between described rebalancing system anolyte liquid storage tank and described positive pole；Described rebalancing system cathode electrolyte storage tank is connected with described negative pole by negative pole circulation line, and negative pole circulating pump is for circulation conveying electrolyte liquid between described rebalancing system cathode electrolyte storage tank and described negative pole；
Wherein, described rebalancing system anolyte liquid storage tank is for storing the anode electrolyte containing active cation；Described rebalancing system cathode electrolyte storage tank is simultaneously as the positive pole storage tank of described treatment fluid flow battery, for storing the anode electrolyte of described treatment fluid flow battery；Wherein, described flow battery rebalancing system is only charged after starting。
2. a Fe-Cr flow battery rebalancing system, reequilibrate for the circulation volume of Fe-Cr flow battery, described Fe-Cr flow battery rebalancing system has the structure of flow battery, including: rebalancing system anolyte liquid storage tank, rebalancing system cathode electrolyte storage tank, positive pole circulating pump, negative pole circulating pump, circulation line and valve, power supply, rebalance cell heap and circuit thereof；Wherein, described rebalance cell heap includes: positive pole, negative pole and ionic membrane；
It is characterized in that: described rebalancing system anolyte liquid storage tank is connected with described positive pole by positive pole circulation line, described rebalancing system anolyte liquid storage tank is for storing the Fe as anode electrolyte2+The electrolyte of initial concentration, it can be delivered to described positive pole by positive pole circulating pump, is then return in described rebalancing system anolyte liquid storage tank；Described rebalancing system cathode electrolyte storage tank is connected with described negative pole by negative pole circulation line, described rebalancing system cathode electrolyte storage tank is simultaneously as the positive pole storage tank of described Fe-Cr flow battery, for storing the anode electrolyte of described Fe-Cr flow battery；Negative pole circulating pump, for the anode electrolyte of described Fe-Cr flow battery is delivered to described negative pole, is then return in described rebalancing system cathode electrolyte storage tank；
Wherein, described Fe-Cr flow battery rebalancing system is only charged after starting。
3. a flow battery system, it is characterised in that include treatment fluid flow battery and flow battery rebalancing system according to claim 1；After the charge and discharge cycles capacity monitoring described treatment fluid flow battery is substantially decayed, start described flow battery rebalancing system and be charged, continuous service until described treatment fluid flow battery anode electrolyte in active cation concentration recover；Active cation concentration in the anode electrolyte of described treatment fluid flow battery closes described flow battery rebalancing system after recovering。
4. a Fe-Cr flow battery system, it is characterised in that include Fe-Cr flow battery and Fe-Cr flow battery rebalancing system according to claim 2；After the charge and discharge cycles capacity monitoring described Fe-Cr flow battery is substantially decayed, start described Fe-Cr flow battery rebalancing system and be charged, continuous service until described Fe-Cr flow battery anode electrolyte in Fe2+Concentration is recovered；Fe in the anode electrolyte of described Fe-Cr flow battery2+Concentration closes described Fe-Cr flow battery rebalancing system after recovering。
5. the method for a flow battery circulation volume reequilibrate, it is characterised in that described method adopts flow battery system according to claim 3, and comprises the following steps:
(1) after the charge and discharge cycles capacity monitoring described treatment fluid flow battery is substantially decayed, start described flow battery rebalancing system immediately to be charged: connect described power supply, and by the valve opening on described positive pole circulation line, by described positive pole circulating pump, anode electrolyte is delivered to described positive pole from described rebalancing system anolyte liquid storage tank, cation in described anode electrolyte, after positive pole completes betatopic, is back to described rebalancing system anolyte liquid storage tank；Simultaneously by the valve opening on described negative pole circulation line, by described negative pole circulating pump, electrolyte liquid is delivered to described negative pole from described rebalancing system cathode electrolyte storage tank, cation in described electrolyte liquid negative pole complete after electronics, be back to described rebalancing system cathode electrolyte storage tank；
(2) it is performed continuously over charging until the active cation concentration in the anode electrolyte of described treatment fluid flow battery is recovered；Active cation concentration in the anode electrolyte of described treatment fluid flow battery closes described flow battery rebalancing system after recovering；
(3) step (1)～(2) are repeated, until when the active cation concentration in the anode electrolyte detected in described rebalancing system anolyte liquid storage tank is low to moderate default replacing value, change this anode electrolyte, be then carried out step (1)。
6. method according to claim 5, it is characterised in that described valve is butterfly valve or ball valve。
7. method according to claim 5, it is characterised in that described flow battery system adopts PLC to control。
8. the method for a Fe-Cr flow battery circulation volume reequilibrate, it is characterised in that described method adopts Fe-Cr flow battery system according to claim 4, and comprises the following steps:
(1) after the charge and discharge cycles capacity monitoring described Fe-Cr flow battery is substantially decayed, start described Fe-Cr flow battery rebalancing system immediately to be charged: connect described power supply, and by the valve opening on described positive pole circulation line, by described positive pole circulating pump, anode electrolyte is delivered to described positive pole, the Fe in described anode electrolyte from described rebalancing system anolyte liquid storage tank2+After positive pole completes betatopic, it is back to described rebalancing system anolyte liquid storage tank；Simultaneously by the valve opening on described negative pole circulation line, by described negative pole circulating pump, electrolyte liquid is delivered to described negative pole, the Fe in described electrolyte liquid from described rebalancing system cathode electrolyte storage tank3+Negative pole complete after electronics, be back to described rebalancing system cathode electrolyte storage tank；
(2) be performed continuously over charging until described Fe-Cr flow battery anode electrolyte in Fe2+Concentration is recovered；Fe in the anode electrolyte of described Fe-Cr flow battery2+Concentration closes described Fe-Cr flow battery rebalancing system after recovering；
(3) step (1)～(2) are repeated, until the Fe in the anode electrolyte detected in the anolyte liquid storage tank of described Fe-Cr flow battery rebalancing system2+When concentration is low to moderate default replacing value, change this anode electrolyte, be then carried out step (1)。
9. method according to claim 8, it is characterised in that described valve is butterfly valve or ball valve。
10. method according to claim 8, it is characterised in that described Fe-Cr flow battery system adopts PLC to control。
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