CN207426026U - A kind of four storage tank flow battery structures for improving electrolyte utilization rate - Google Patents

A kind of four storage tank flow battery structures for improving electrolyte utilization rate Download PDF

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CN207426026U
CN207426026U CN201721496998.4U CN201721496998U CN207426026U CN 207426026 U CN207426026 U CN 207426026U CN 201721496998 U CN201721496998 U CN 201721496998U CN 207426026 U CN207426026 U CN 207426026U
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electrolyte
liquid
fluid reservoir
storage tank
flow battery
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刘柏辰
郑梦莲
孙洁
赵俊雄
田帅奇
王涛
张良
范利武
俞自涛
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The utility model discloses a kind of four storage tank flow battery structures for improving electrolyte utilization rate, belong to new energy energy storage field.The utility model connects an independent fluid reservoir respectively compared with traditional flow battery, in anode electrolyte inlet, electrolyte liquid inlet, anode electrolyte liquid outlet and electrolyte liquid liquid outlet, makes feed liquor and goes out liquid not in formation cycle.In the electric flow cell design of the utility model, the utilization rate of positive and negative anodes electrolyte dramatically increases, and the difference of electrolyte state-of-charge between battery pile and fluid reservoir can be greatly lowered, and reduces the concentration polarization between pile and fluid reservoir.And the prolonged charge and discharge of battery can be still kept in the case of low flow velocity, it can be applied in the occasion of current density bigger, keep battery working properly.In the case where the volume of fluid reservoir is larger, it can guarantee that liquid energy is electrolysed in fluid reservoir keeps good uniformity, electrolyte in traditional two tank structures avoided to mix the uneven influence brought to battery.

Description

A kind of four storage tank flow battery structures for improving electrolyte utilization rate
Technical field
The utility model belongs to new energy energy storage field, and in particular to a kind of four storage tank liquid streams for improving electrolyte utilization rate Battery structure.
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, cause its stability and continuity poor, simultaneously Also more serious impact can be generated 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, peak load shifting is realized, and then realizes 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, research and development, 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 external fluid reservoir.Traditional flow battery structure is by two Xun Huans 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, and forming 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 rate 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 state-of-charge (SoC) of battery increases, during electric discharge, battery State-of-charge (SoC) reduces.In flow battery, the electricity of entire battery system is depended in the capacity and electrolyte of fluid reservoir The concentration of active ion, and its peak power is then determined by the total surface area of battery.
As shown in fig. 7, the method for operation of traditional flow battery using two storage tanks:First, stored up in positive and negative anodes electrolyte Isometric electrolyte is added in flow container, battery carries out charging process first after bringing into operation, positive and negative anodes electrolyte passes through respectively Circulating pump enters the pile region of battery, and redox reaction occurs at the electrode surface, makes the state-of-charge of electrolyte (SoC) increase, the subsequent increased electrolyte outflow pile of state-of-charge (SoC) comes back to positive and negative anodes electrolyte liquid storage respectively In tank, the electrolyte of state-of-charge (SoC) low with fluid reservoir mixes, and the cycling of electrolyte is carried out with this, until in pile Voltage reaches charge cutoff voltage.Discharge process is then carried out, the state-of-charge (SoC) of electrolyte continuously decreases, until pile In voltage reach discharge cut-off voltage, complete a charge and discharge cycles.
However, also it there are problems that in two current tank structures.Applicant is by the study found that in liquid stream electricity During the charge and discharge of pond, the state-of-charge (SoC) of electrolyte will be different between pile and storage tank, especially in low flow velocity In the case of difference between the two can be clearly.This species diversity mainly due to:When the electrolyte of highly charged state flows out During pile, the electrolyte of meeting state-of-charge low with storage tank mixes, and the time difference during this can cause electricity in storage tank The state-of-charge for solving liquid can the permanent state-of-charge less than electrolyte in pile.When flow velocity is very small, difference will be very Substantially.Since the charge and discharge blanking voltage of battery is judged according to the state-of-charge collected in pile, this Species diversity will seriously affect the utilization rate of electrolyte.In other words, when the state-of-charge of electrolyte in pile is already higher than charging During blanking voltage, the state-of-charge of electrolyte is also very low in storage tank, this just has the electrolyte of the overwhelming majority not to be utilized. Seeking to reduce or eliminate the method for electrolyte state-of-charge difference between pile and storage tank as a result, seems particularly urgent, this is favourable In the current density that charging can be improved in the case of low flow velocity, to improve the response performance of flow battery.
The content of the invention
The purpose of this utility model is that solving problems of the prior art, and propose that a kind of raising electrolyte utilizes Four storage tank flow battery structures of rate in the conversion of flow battery energy energy, reduce the state-of-charge between pile and storage tank Difference increases substantially the utilization rate of electrolyte.
And the four storage tank flow batteries of the utility model are to be achieved through the following technical solutions:
Four storage tank flow battery structures of electrolyte utilization rate are improved, are had just on the pile end plate of the flow battery both sides Pole electrolyte inlet, electrolyte liquid inlet, anode electrolyte liquid outlet and electrolyte liquid liquid outlet, further include anode Electrolyte feed liquor fluid reservoir, electrolyte liquid feed liquor fluid reservoir, anode electrolyte go out liquid fluid reservoir and electrolyte liquid goes out liquid storage Flow container, the anode electrolyte inlet connect anode electrolyte feed liquor fluid reservoir, the negative electricity by infusion pipeline It solves liquid inlet and electrolyte liquid feed liquor fluid reservoir is connected by infusion pipeline, the anode electrolyte liquid outlet passes through infusion Pipeline connection anode electrolyte goes out liquid fluid reservoir, and the electrolyte liquid liquid outlet connects electrolyte liquid by infusion pipeline Go out liquid fluid reservoir;The infusion pump that electrolyte in promising pipeline provides two-way flow power is all provided on each infusion pipeline, it is each to store up The liquid level sensor of liquid level in sensing tank is equipped in flow container.
Preferably, the infusion pipeline end extends the minimum point of each storage tank interior.
Preferably, the infusion pump is two-way pump.
Preferably, the electric pile structure of flow battery is:It is clamped with several 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, collector plate is additionally provided in pile.
Further, the collector plate is circumscribed with charge-discharge system.
Preferably, the flow battery is all-vanadium flow battery, zinc-bromine flow battery or Zn-Ni liquid battery.
Preferably, the infusion pump uses wriggling circulating pump.
The utility model compared with prior art, has following features:First, the utilization rate of positive and negative anodes electrolyte significantly increases Add, the difference of electrolyte state-of-charge (SoC) between battery pile and fluid reservoir can be greatly lowered, reduce pile and fluid reservoir Between concentration polarization.Second, the prolonged charge and discharge of battery can be still kept in the case of low flow velocity, can be applied to electricity In the occasion of current density bigger, keep battery working properly.3rd, in the case where the volume of fluid reservoir is larger, it can guarantee storage Liquid energy is electrolysed in flow container and keeps good uniformity, avoids in traditional two tank structures that electrolyte mixing is uneven to bring battery Influence.
Description of the drawings
Fig. 1 is that a kind of four storage tank flow batteries of raising electrolyte utilization rate are basic in the utility model specific implementation example Schematic diagram.
Fig. 2 is the schematic diagram of the positive and negative anodes electrolyte inlet of Fig. 1 described devices in the utility model.
Fig. 3 is the schematic diagram of the positive and negative anodes electrolyte liquid outlet of Fig. 1 described devices in the utility model.
Fig. 4 is electrolyte utilization rate in two storage tanks in the utility model and four tank structures with the pass between flow rate β System.
Fig. 5 be two storage tanks between pile (Stack) and fluid reservoir (Tank) electrolyte state-of-charge with flow rate β's Difference.
Fig. 6 be four storage tanks between pile (Stack) and fluid reservoir (Tank) electrolyte state-of-charge with flow rate β's Difference.
Fig. 7 is that traditional two tank structures and electrolyte cycle schematic diagram.
In figure:Pile end plate 1, pile PP plates 2, single-cell structure unit 3, infusion pipeline 4, infusion pump 5, anode electrolyte Feed liquor fluid reservoir 6, electrolyte liquid feed liquor fluid reservoir 7, anode electrolyte goes out liquid fluid reservoir 8, and electrolyte liquid goes out liquid fluid reservoir 9, liquid level sensor 10, anode electrolyte inlet 11, electrolyte liquid inlet 12, collector plate 13, bolt hole 14, anode electricity Solve liquid liquid outlet 15, electrolyte liquid liquid outlet 16.
Specific embodiment
The utility model is further elaborated and illustrated with reference to the accompanying drawings and detailed description.In the utility model The technical characteristic of each embodiment can carry out respective combination on the premise of not conflicting with each other.
As shown in Figures 1 to 3, in embodiment, four storage tank flow battery structures of electrolyte utilization rate are improved, are broadly divided into The pile part of battery and the outer circulating section of electrolyte, critical piece include pile end plate 1, pile PP plates 2, monocell Structural unit 3, infusion pipeline 4, infusion pump 5, anode electrolyte feed liquor fluid reservoir 6, electrolyte liquid feed liquor fluid reservoir 7, anode Electrolyte goes out liquid fluid reservoir 8, and electrolyte liquid goes out liquid fluid reservoir 9, sensor 10, anode electrolyte inlet 11, electrolyte Liquid inlet 12, collector plate 13, bolt hole 14, anode electrolyte liquid outlet 15, electrolyte liquid liquid outlet 16.
Mainly (polyethylene material can be used by pile end plate 1 (stainless steel end plate can be used), PP plates 2 in the pile part of battery 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 14 is opened up for being 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 13 (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 current transmission for connecing power supply enters 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 Cathode transfers hydrogen ion and hydrone, keeps the charge balance of battery) etc. critical pieces.
There is anode electrolyte inlet 11, electrolyte liquid inlet 12, just on the pile end plate 1 of flow battery both sides Pole electrolyte liquid outlet 15 and electrolyte liquid liquid outlet 16.Each entry/exit liquid mouth corresponds to each single-cell structure list in connection pile The positive or negative pole conversion zone of member 3, can carry out charged/discharge process on the electrode in these regions.
The outer circulating section of electrolyte mainly includes anode electrolyte feed liquor fluid reservoir 6, electrolyte liquid feed liquor liquid storage Tank 7, anode electrolyte go out liquid fluid reservoir 8 and electrolyte liquid goes out liquid fluid reservoir 9.Anode electrolyte inlet 11 passes through woven hose Road 4 connects anode electrolyte feed liquor fluid reservoir 6, and electrolyte liquid inlet 12 connects electrolyte liquid feed liquor by infusion pipeline Fluid reservoir 7, anode electrolyte liquid outlet 15 connect anode electrolyte by infusion pipeline 4 and go out liquid fluid reservoir 8, and electrolyte liquid goes out Liquid mouth 16 connects electrolyte liquid by infusion pipeline 4 and goes out liquid fluid reservoir 9.Electrolyte conveying has to flow through electricity between each fluid reservoir Heap, there is no other direct switching channels.Electrolyte in promising pipeline is all provided on each infusion pipeline 4, two-way flow power is provided Infusion pump 5, infusion pump 5 using the conveying that can commutate two-way pump (wriggling circulating pump can be used).In addition, in each fluid reservoir Be all provided with there are one sensing tank in liquid level liquid level sensor 10, liquid level sensor 10 can be used photoelectric level transducer, The forms such as sound wave type liquid level sensor, float type liquid level sensor or fluid pressure type sensor.For the ease of automatically controlling, also may be used In addition to set the automaton in the form of microcontroller, a PLC etc., it is connected with equipment such as collector 13, infusion pumps 5.
The flow battery structure changes two traditional storage tank forms, and anode electrolyte/electrolyte liquid is each used Two storage tanks are stored, the electrolyte in a storage tank be delivered to it is charged in pile after, no longer return to the storage tank, but It flows into another storage tank to be stored, electrolyte state-of-charge (SoC) between battery pile and fluid reservoir is thus greatly lowered Difference.When collector 13 detects charge cutoff voltage, the state-of-charge of electrolyte basically reaches voltage correspondence in pile State, when electric discharge is as the same.In contrast, electrolyte utilizes for four tank structures of the utility model and two traditional tank structures Rate, electrolyte state-of-charge as shown in figures 4-6, show four storage tanks of the utility model with the variation relation between flow rate β In the case of effectively preventing low flow velocity, the difference of state-of-charge, substantially increases in flow battery and is electrolysed between storage tank and pile The utilization rate of liquid.
Based on the flow battery structure, improving the basic principle of electrolyte utilization rate makes in a storage tank (being denoted as A) After electrolyte flows into pile, storage tank A is no longer recycled back to immediately, and is stored in another independent storage tank (being denoted as B), until storage Electrolyte in tank A fully enters that pile is charged to be finished;The infusion direction of infusion pump is adjusted at this time, is changed to from storage tank B to electricity Heap input electrolyte continue it is charged, it is charged after electrolyte be stored in storage tank A.For the anode electrolyte and negative electricity of pile Solution liquid constantly repeats the cyclic process, until reaching charge cutoff voltage, completing charging process and entering discharge process.It discharged Cheng Zhong also repeats the cycling, until reaching discharge cut-off voltage, completes discharge process.Thus a charge and discharge cycles are formed.
The specific method for improving electrolyte utilization rate is described below in detail, step is as follows:
Isometric electrolyte is added in anode electrolyte feed liquor fluid reservoir 6 and electrolyte liquid feed liquor fluid reservoir 7 first, Two infusion pumps 5 of control inlet one side are rotated counterclockwise (in the present embodiment on the basis of direction in Fig. 1, as long as actual energy The electrolyte of the side is enough made to input pile), two infusion pumps 5 of liquid outlet one side are not run, and are respectively electrolysed positive and negative anodes Liquid is transported to anode electrolyte inlet 11 and electrolyte liquid inlet 12 by infusion pipeline 4, passes sequentially through pile end plate 1 Enter with pile PP plates 2 in the single-cell structure unit 3 in pile, it is anti-that redox occurs on the electrode surface of each monocell Should, the state-of-charge (SoC) of electrolyte can increase after reaction.Positive and negative anodes electrolyte after state-of-charge increase is respectively from anode electricity Solution liquid liquid outlet 15 and electrolyte liquid liquid outlet 16 flow out, and are flowed into anode electrolyte and go out liquid fluid reservoir 8 and electrolyte liquid Go out in liquid fluid reservoir 9.When two sensors 10 of feed liquor one side detect anode electrolyte feed liquor fluid reservoir 6 and electrolyte liquid Two sensors 10 that electrolyte in feed liquor fluid reservoir 7 has exhausted or gone out liquid one side detect that anode electrolyte goes out liquid When the electrolyte that fluid reservoir 8 and electrolyte liquid go out in liquid fluid reservoir 9 has filled up, two infusion pumps of control inlet one side 5 do not run, and two infusion pumps 5 of liquid outlet one side rotate clockwise (in the present embodiment on the basis of direction in Fig. 1, actually only The electrolyte of the side can be made to input pile), i.e. the inlet of script is converted into liquid outlet, the liquid outlet conversion of script For inlet, electrolyte is reentered in the single-cell structure unit 3 in pile.And so on by electrolyte in four storage tanks Reciprocation cycle.(charge cutoff voltage can be set when the voltage that collector plate 13 collects battery has reached charge cutoff voltage For 1.7V), it charges and terminates to start discharge process, electrolyte still keeps reciprocation cycle in four storage tanks at this time, until afflux (it is 0.8V that can set discharge cut-off voltage), discharge process when the voltage that plate 13 collects battery has reached discharge cut-off voltage Terminate, complete a charge and discharge cycles, then proceed by subsequent charge and discharge cycles.
It should be noted that in above process, the conveying speed of anode electrolyte and negative electrode liquid need to be consistent. In addition, in order to avoid the occurrence of the difference of electrolyte state-of-charge (SoC) between battery pile and fluid reservoir, infusion pipeline as far as possible End need to extend the minimum point of each storage tank interior, and the electrolyte in tank is made to be fully entered as far as possible in pile.It is and each Liquid storage tank volume should try one's best greatly, and when the fluid reservoir that electrolyte outflow end had better not occur is filled, electrolyte flows into the storage at end Still there is the remaining situation of electrolyte in flow container.
Embodiment described above is a kind of preferable scheme of the utility model, and so it is not to limit this practicality It is new.Those of ordinary skill in technical field, can be in the case where not departing from the spirit and scope of the utility model It makes a variety of changes and modification.For example, various modes of the prior art may be employed in the concrete structure of flow battery, and it is unlimited Due to the structure described in embodiment.Therefore the technical solution that all modes for taking equivalent substitution or equivalent transformation are obtained, Fall within the protection scope of the present utility model.

Claims (7)

1. a kind of four storage tank flow battery structures for improving electrolyte utilization rate, have on the pile end plate (1) of flow battery both sides There are anode electrolyte inlet (11), electrolyte liquid inlet (12), anode electrolyte liquid outlet (15) and electrolyte liquid Liquid outlet (16), which is characterized in that further include anode electrolyte feed liquor fluid reservoir (6), electrolyte liquid feed liquor fluid reservoir (7), Anode electrolyte goes out liquid fluid reservoir (8) and electrolyte liquid goes out liquid fluid reservoir (9), and the anode electrolyte inlet (11) is logical Infusion pipeline connection anode electrolyte feed liquor fluid reservoir (6) is crossed, the electrolyte liquid inlet (12) passes through infusion pipeline Electrolyte liquid feed liquor fluid reservoir (7) is connected, the anode electrolyte liquid outlet (15) connects anode electricity by infusion pipeline Solution liquid goes out liquid fluid reservoir (8), and the electrolyte liquid liquid outlet (16) connects electrolyte liquid by infusion pipeline and goes out liquid storage Flow container (9);The infusion pump (5) that electrolyte in promising pipeline provides two-way flow power is all provided on each infusion pipeline, it is each to store up The liquid level sensor (10) of liquid level in sensing tank is equipped in flow container.
2. four storage tank flow battery structures of electrolyte utilization rate are improved as described in claim 1, which is characterized in that described Infusion pipeline end extends the minimum point of each storage tank interior.
3. four storage tank flow battery structures of electrolyte utilization rate are improved as described in claim 1, which is characterized in that described Infusion pump is two-way pump.
4. four storage tank flow battery structures of electrolyte utilization rate are improved as described in claim 1, which is characterized in that liquid stream electricity The electric pile structure in pond is:Several single-cell structure units (3) are clamped between both sides PP plates (2), are fixed respectively outside the PP plates of both sides There is pile end plate (1), collector plate (13) is additionally provided in pile.
5. four storage tank flow battery structures of electrolyte utilization rate are improved as claimed in claim 4, which is characterized in that described Collector plate (13) is circumscribed with charge-discharge system.
6. four storage tank flow battery structures of electrolyte utilization rate are improved as described in claim 1, which is characterized in that described Flow battery is all-vanadium flow battery, zinc-bromine flow battery or Zn-Ni liquid battery.
7. four storage tank flow battery structures of electrolyte utilization rate are improved as described in claim 1, which is characterized in that described Infusion pump (5) uses wriggling circulating pump.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107946617A (en) * 2017-11-10 2018-04-20 浙江大学 A kind of four storage tank flow battery structures and method for improving electrolyte utilization rate
CN114566683A (en) * 2022-03-03 2022-05-31 南京畅晟能源科技有限公司 Multifunctional zinc-bromine flow battery cell stack testing device and testing method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107946617A (en) * 2017-11-10 2018-04-20 浙江大学 A kind of four storage tank flow battery structures and method for improving electrolyte utilization rate
CN107946617B (en) * 2017-11-10 2023-06-02 浙江大学 Four-storage-tank flow battery structure and method for improving electrolyte utilization rate
CN114566683A (en) * 2022-03-03 2022-05-31 南京畅晟能源科技有限公司 Multifunctional zinc-bromine flow battery cell stack testing device and testing method thereof
CN114566683B (en) * 2022-03-03 2023-08-11 南京畅晟能源科技有限公司 Multifunctional zinc-bromine flow battery pile testing device and testing method thereof

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