CN102780018A - Integrated liquid storage pot and novel zinc-bromine redox flow battery - Google Patents
Integrated liquid storage pot and novel zinc-bromine redox flow battery Download PDFInfo
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- CN102780018A CN102780018A CN2012102868626A CN201210286862A CN102780018A CN 102780018 A CN102780018 A CN 102780018A CN 2012102868626 A CN2012102868626 A CN 2012102868626A CN 201210286862 A CN201210286862 A CN 201210286862A CN 102780018 A CN102780018 A CN 102780018A
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Abstract
The invention discloses a structure and a fabrication method of an integrated liquid storage pot, and a novel zinc-bromine redox flow battery. The novel zinc-bromine redox flow battery comprises a liquid storage pot 1, a liquid supply pump A2, a liquid supply pump B3, an anode pipeline system 41, a cathode pipeline system 42, a galvanic pile 5, an anode return pipe 71 and a cathode return pipe 72; the liquid storage pot 1 is connected to the liquid supply pump A2, the liquid supply pump B3, the anode return pipe 71 and the cathode return pipe 72, respectively; the galvanic pile 5 is connected to the anode pipeline system 41, the cathode pipeline system 42, the anode return pipe 71 and the cathode return pipe 72, respectively; the liquid supply pump B3 is connected to the anode pipeline system 41; and the liquid supply pump A2 is connected to the anode pipeline system 41 and the cathode pipeline system 42. The anode and the cathode of the battery are connected back to the same liquid storage pot 1, so that the migration problem is fundamentally solved; the system is simple and the fault rate is low; and the same liquid supply pumps are adopted for supplying liquid so that the pressure on the two sides of the anode and cathode pipeline systems is balanced, and the deformation rate of the material is reduced.
Description
Technical field
The present invention relates to a kind of integrated fluid reservoir and new zinc bromine flow battery, belong to the flow battery field.
Background technology
Along with the continuous deterioration of global environment and people attention to environmental problem; The eco-friendly clean energy resource of development of new is extremely urgent; Redox flow batteries (Redox flow battery) is a kind of energy-storage system of rising in recent years, and it has common batteries and fuel cell performance concurrently, has working life and storage life long; Advantage such as fast charging and discharging, depth of discharge performance are good; Airtight circulating system has been avoided contacting with the external world simultaneously, has avoided the pollution to environment, and electrode material needn't use valuable metallic catalyst etc.Therefore, realize the scale high-efficiency energy-storage, accelerate economic development that it is significant to develop redox flow batteries.
Zinc bromine redox flow batteries is a kind of of redox flow batteries, and electrolyte is the zinc bromide aqueous solution, and in the charging process, zinc is deposited on electrode surface with metal form, and bromine forms the oily complex compound, is stored in the bottom of anodal electrolyte.The theoretical open circuit voltage 1.82V of zinc bromine flow battery, gross efficiency is 75%, theoretical energy density 430Wh/kg, battery can 100% deep discharges thousands of times, compare with lead-acid battery, have high energy density and power density and superior cycle charge discharge electrical property.Zinc-bromine bettery is worked under near ambient temperature, do not need complicated thermal control system, and the cost of raw material is cheap, makes it become one of selection of extensive energy-storage battery.
Zinc bromine flow battery also exists some technical problems, uses micro-pore septum like battery, and in the battery operation process, electrolyte moves, and causes both positive and negative polarity electrolyte not match, and influences battery performance.When the migration amount was big, high-order side electrolyte liquid level rose to fluid reservoir mouth place, made electrolyte reveal owing to pressure possibly cause seal failure; The low level side is because of the suction Cheng Zengjia of solution feed pump, possibly cause the pump overload and damages.Therefore, the electrolyte migration problem also seriously influences battery life.
Cause the reason of electrolyte migration a lot, typical, as:
1, the pressure reduction in the both positive and negative polarity pipeline;
2, the migration that the both sides concentration difference is brought in the barrier film;
Carry the migration that water yield difference causes when 3, ion moves.
Traditional way is through both sides pump frequency modulation, changes the both sides liquid supply pressure, thereby reaches the purpose of regulating liquid level.But there is following shortcoming in this method:
1. system complex, failure rate is high;
2. people's pump pressure for a change in the adjustment process has certain influence to battery performance;
3. electrolyte is regulated through the artificial both positive and negative polarity pressure reduction of making, and can increase the material deformation rate;
4. limited by operating mode when regulating, might can't realize;
5. for making pressure reduction, need extra energy, make system effectiveness reduce.
Summary of the invention
The objective of the invention is to; A kind of structure, manufacture method and new zinc bromine flow battery of integrated fluid reservoir are provided, and it can effectively solve the problem that exists in the prior art, particularly electrolyte migration; Cause both positive and negative polarity electrolyte coupling inhomogeneous, influence the performance of battery and the problem in life-span.
For solving the problems of the technologies described above; The present invention adopts following technical scheme: a kind of integrated fluid reservoir; Comprise: tank body, confession bromine pipeline, total return duct and feed pipe; An end that supplies the bromine pipeline is through the sidewall of tank body and be positioned at tank body, and an end of total return duct and feed pipe is through the top of tank body and be positioned at the top of tank base.
In the aforesaid integrated fluid reservoir, also be provided with deflection plate and base plate in the described tank body, an end of base plate is connected near a side that supplies the bromine pipeline with the tank body bottom surface and the angle of base plate and tank body bottom surface is 5 °～10 °; Deflection plate is located between base plate and the feed pipe, and an end of total return duct is through deflection plate and be positioned at the top of base plate, and the angle of deflection plate and horizontal plane is 0 °～30 °, and a deflection plate end nearer apart from horizontal plane is provided with spout hole; When the angle of deflection plate and horizontal plane is 0 °; Any end that spout hole is located at deflection plate all can; Thereby can effectively prevent the self-discharge phenomenon that both positive and negative polarity electrolyte produces in integrated fluid reservoir, the performance and the useful life of the flow battery that this integrated fluid reservoir of raising application is made into.
In the above-mentioned integrated fluid reservoir, the angle between deflection plate and base plate and the tank base is big more, and is obvious more to the effect that refluxed mutually by the high density that sub-elected, but the velocity component of corresponding vertical direction is also big more, and tank body volume and weight are also had certain influence.Deflection plate works to increase electrolyte flow path in fluid reservoir, simultaneously the high density that is gone out by gravity separation is had mutually the effect of the guiding of refluxing.
Described spout hole can compensate upper strata electrolyte, and promptly supernatant liquor is taken away, behind electrode surface generation chemical reaction, is back near the fluid reservoir bottom by total return duct, cause the bottom near pressure raise, electrolyte is moving to upper stream by lower floor.
In the aforesaid integrated fluid reservoir; The angle of described deflection plate and horizontal plane is 5 °; The angle of base plate and tank body bottom surface is 5 °, thereby the resultant effect of velocity component, tank body volume and the weight of the backflow effect of the feasible high density phase that is sub-elected, vertical direction is best.
In the aforesaid integrated fluid reservoir, said number of baffles is one deck at least, and when number of baffles during greater than one deck, adjacent two-layer deflection plate surrounds a ladder cavity arbitrarily, thereby can further improve the effect of bromine sorting.
In the aforesaid integrated fluid reservoir, the narrow end of ladder cavity is located on the tank body near a side that supplies the bromine pipeline, thereby makes that the flow path of electrolyte is the longest, and is best to the separating effect of bromine simple substance, complexing bromine and electrolyte clear liquid.
In the aforesaid integrated fluid reservoir, described spout hole both sides also are provided with magnetic material, utilize magnetic field to produce positive coopertive effect, can assist and improve separating effect and not extra consumption.
Described magnetic material is general permanent magnet, and like magnet, its magnetic field intensity is smaller or equal to 1T; If the magnetic field intensity of magnetic material is during greater than 1T, then magnetic field not only can not make separating effect improve as auxiliary sorting structure, has also increased cost and weight on the contrary; In addition, if the magnetic field intensity of magnetic material is greater than 1T, magnetic field intensity is excessive, possibly impact jar outer electronic component (like transducer) and equipment (like pump).
Preferably, the magnetic field intensity of magnetic material is smaller or equal to 3000 Gausses.
Described magnetic material is by plastic wraps, thereby prevents that magnetic material is corroded.
Described spout hole accounts for 50% of deflection plate width, if spout hole is too small, may bring bigger change in flow when then liquid is through spout hole, thereby influence separating effect, but also may increase energy consumption; If spout hole is excessive, then the auxiliary separating effect of magnetic material can descend.
In the aforesaid integrated fluid reservoir; Described total return duct is located at the nearer side of distance confession bromine pipeline on the tank body, owing to supply the bromine pipeline to be positioned at the least significant end of tank wall, belongs to the bromine enrichment region; In charging process; The anodal bromine that produces can directly be back to this zone with total return duct, and the convection current of minimizing and electrolyte improves separating effect; During discharge, always reflux liquid in pipe when pipeline is discharged, itself have certain flow velocity; This flow velocity can be so that disturbance takes place in " the pure bromine " of bromine enrichment region; Through supplying the bromine pipeline to extract the bromine mixed solution, help bromine in electrode solution, to disperse, reduce the pressure that supplies the bromine pipeline simultaneously; Reduce the pump consumption, improve battery life; In addition, in the discharge process unreacted completely bromine get back to the bromine enrichment region with shortest path, reduce convection current, further improved separating effect.
A kind of manufacture method of integrated fluid reservoir adopts methods such as sheet material sweat soldering, blowing or rotational moulding to be made, and the technological parameter that wherein is specifically related to is decided according to sheet material.
The new zinc bromine flow battery that utilizes aforesaid integrated fluid reservoir to be made into; Comprise fluid reservoir, solution feed pump A, solution feed pump B, anodal pipe-line system, negative pole pipe-line system, pile, anodal return duct and negative pole return duct; Fluid reservoir is connected with solution feed pump A, solution feed pump B, anodal return duct and negative pole return duct respectively; Pile is connected with anodal pipe-line system, negative pole pipe-line system, anodal return duct and negative pole return duct respectively; Solution feed pump B is connected with anodal pipe-line system, and solution feed pump A is connected with the negative pole pipe-line system with anodal pipe-line system respectively.
In the aforesaid new zinc bromine flow battery, in the described fluid reservoir, an end that supplies the bromine pipeline is through the sidewall of tank body and be positioned at tank body; The other end is connected with solution feed pump B, and an end of total return duct is through the top of tank body and be located at the top of tank base, and the other end is connected with the negative pole return duct with anodal return duct respectively; One end of feed pipe is through the top of tank body and be located at the top of tank base; The other end is connected with solution feed pump A, and solution feed pump B quits work when charging, when discharge, starts; Reduce system energy consumption and self discharge amount, thereby improved the operating efficiency of zinc bromine flow battery; Reacted both positive and negative polarity electrolyte can flow and behind total return duct, be back to integrated fluid reservoir, has fundamentally solved the problem of electrolyte migration; Electrolyte pumps from same pump (solution feed pump A), branches to both positive and negative polarity, because the loine pressure of shunting side is identical, thereby has reduced the both positive and negative polarity total pressure head.
In the aforesaid new zinc bromine flow battery; Also comprise: heat-exchange system, described heat-exchange system comprises: heat exchanger and cooler, cooler is connected with heat exchanger; Heat exchanger is connected with anodal return duct, negative pole return duct or fluid reservoir; Heat exchanger is emitted at cooler after absorbing heat, thereby can effectively reduce the temperature of electrolyte.
In the aforesaid new zinc bromine flow battery, described cooler is connected with heat exchanger, and heat exchanger is connected with fluid reservoir, thereby makes the cooling-down effect to electrolyte reach best.
Compared with prior art, the present invention has the following advantages:
1. design integrated fluid reservoir, made both positive and negative polarity electrolyte get back in the identical storage tank, be pumped out again, fundamentally solved the problem of electrolyte migration;
2. through the spout hole on design deflection plate, base plate and the deflection plate; Thereby can utilize gravity separation to make bromine simple substance, complexing bromine separate with the electrolyte clear liquid; In addition, deflection plate is designed to one deck at least, when the time greater than one deck; Adjacent two-layer deflection plate surrounds a ladder cavity and in the both sides of spout hole magnetic material is set arbitrarily; Counteracting or reduction be the velocity component of (opposite with gravity direction) straight up, makes fluid slowly flow along the zone of deflection plate, thereby can increase Br
3 -Residence time, further strengthened the effect of gravity separation; Not only need not extra power consumption in the whole assorting room, but also can effectively prevent the self-discharge phenomenon that both positive and negative polarity electrolyte produces in integrated fluid reservoir, the performance and the useful life of the flow battery that this integrated fluid reservoir of raising application is made into;
3. need not management such as electrolyte coupling, both positive and negative polarity pressure coupling, thereby simplified system, reduced the failure rate of system;
4. compare with traditional fluid reservoir, the liquid storage tank structure that the present invention designed is simple, size is little, in light weight, can effectively reduce the danger of electrolyte leakage, improves the energy density of system simultaneously; In addition, traditional fluid reservoir is two jar structures, and the integrated fluid reservoir among the present invention is single jar, the material of use still less, space availability ratio is higher, simultaneously the also corresponding minimizing of area of sealing area;
5. use same solution feed pump (solution feed pump A) to give the both positive and negative polarity feed flow, balance pressure at both sides, reduced the distortion of materials probability, improved the life-span of zinc bromine flow battery simultaneously;
6. solution feed pump B quits work when battery charge, starts during battery discharge, has reduced the system energy consumption and the self discharge amount of zinc bromine flow battery, has improved the energy efficiency of zinc bromine flow battery;
7. after solution feed pump B is pumped into anodal pipe-line system with the bromo-complex of tank base; Natural mixing gets into pile to the electrolyte clear liquid on bromo-complex and upper strata then owing to the effect of flow rate of liquid in pipe-line system inside, compares with conventional art; The present invention has practiced thrift the equipment that plays mixed function that adds in solution feed pump B rear end; Like blender etc., thereby simplify the structure of battery system, practiced thrift cost;
8. the cooler of heat-exchange system is connected with heat exchanger, and heat exchanger is connected with fluid reservoir, because the electrolyte in the storage tank is in stable condition; Basically not receiving to flow influences, and the total thermal capacitance of storage tank electrolyte inside is bigger, and variations in temperature is slow; Control easily, in addition, can be through changing cooling fluid temperature and flow velocity in the heat exchanger; Change system heat requires to reach high energy efficiency point according to heat exchange, and does not influence the stable performance of battery system; Therefore, heat exchanger is best with the heat exchange cooling-down effect that storage tank directly is connected generation.
Description of drawings
Fig. 1 is the structural representation of new zinc bromine flow battery;
Fig. 2 is the structural representation of integrated fluid reservoir;
Fig. 3 is the profile of integrated fluid reservoir;
Fig. 4 is the vertical view of deflection plate;
Fig. 5 is the position view of magnetic material;
Fig. 6 records Br in 25 ℃, the electrolyte of 2.5M
3 -The concentration sketch map.
Reference numeral: 1-fluid reservoir, 2-solution feed pump A, 3-solution feed pump B, the anodal pipe-line system of 41-, 42-negative pole pipe-line system; The 4-feed pipe, 5-pile, 61-heat exchanger, 62-cooler; The anodal return duct of 71-, 72-negative pole return duct, the total return duct of 7-, 8-supplies the bromine pipeline; The 9-spout hole, 10-tank body, 11-deflection plate, 12-base plate.
Below in conjunction with accompanying drawing and embodiment the present invention is further described.
Embodiment
Embodiment 1: a kind of integrated fluid reservoir; As shown in Figure 2; Comprise: tank body 10, confession bromine pipeline 8, total return duct 7 and feed pipe 4; An end that supplies bromine pipeline 8 is through the sidewall of tank body 10 and be positioned at tank body 10, and an end of total return duct 7 and feed pipe 4 is through the top of tank body 10 and be positioned at the top of tank body 10 bottoms.
Embodiment 2: a kind of integrated fluid reservoir; As shown in Figure 2; Comprise: tank body 10, confession bromine pipeline 8, total return duct 7 and feed pipe 4; An end that supplies bromine pipeline 8 is through the sidewall of tank body 10 and be positioned at tank body 10, and an end of total return duct 7 and feed pipe 4 is through the top of tank body 10 and be positioned at the top of tank body 10 bottoms.Also be provided with deflection plate 11 and base plate 12 (as shown in Figure 3) in the described tank body 10, an end of base plate 12 is connected near a side that supplies bromine pipeline 8 with tank body 10 bottom surfaces and the angle of base plate 12 and tank body 10 bottom surfaces is 5 °; Deflection plate 11 is located between base plate 12 and the feed pipe 4; One end of total return duct 7 is through deflection plate 11 and be positioned at the top of base plate 12; Deflection plate 11 is 5 ° with the angle of horizontal plane, and deflection plate 11 end nearer apart from horizontal plane is provided with spout hole 9 (as shown in Figure 4).
Embodiment 3: a kind of integrated fluid reservoir; Comprise: tank body 10, confession bromine pipeline 8, total return duct 7 and feed pipe 4; An end that supplies bromine pipeline 8 is through the sidewall of tank body 10 and be positioned at tank body 10, and an end of total return duct 7 and feed pipe 4 is through the top of tank body 10 and be positioned at the top of tank body 10 bottoms.Also be provided with deflection plate 11 and base plate 12 in the described tank body 10, an end of base plate 12 is connected near a side that supplies bromine pipeline 8 with tank body 10 bottom surfaces and the angle of base plate 12 and tank body 10 bottom surfaces is 5 °; Deflection plate 11 is located between base plate 12 and the feed pipe 4, and an end of total return duct 7 is through deflection plate 11 and be positioned at the top of base plate 12, and deflection plate 11 is 5 ° with the angle of horizontal plane, and deflection plate 11 end nearer apart from horizontal plane is provided with spout hole 9.Described spout hole 9 both sides also are provided with magnetic material (as shown in Figure 5).
Embodiment 4: a kind of integrated fluid reservoir; As shown in Figure 2; Comprise: tank body 10, confession bromine pipeline 8, total return duct 7 and feed pipe 4; An end that supplies bromine pipeline 8 is through the sidewall of tank body 10 and be positioned at tank body 10, and an end of total return duct 7 and feed pipe 4 is through the top of tank body 10 and be positioned at the top of tank body 10 bottoms.Also be provided with deflection plate 11 and base plate 12 (as shown in Figure 3) in the described tank body 10, an end of base plate 12 is connected near a side that supplies bromine pipeline 8 with tank body 10 bottom surfaces and the angle of base plate 12 and tank body 10 bottom surfaces is 10 °; Deflection plate 11 is located between base plate 12 and the feed pipe 4; One end of total return duct 7 is through deflection plate 11 and be positioned at the top of base plate 12; Deflection plate 11 is 30 ° with the angle of horizontal plane, and deflection plate 11 end nearer apart from horizontal plane is provided with spout hole 9 (as shown in Figure 4).The quantity of said deflection plate 11 is greater than one deck, and adjacent two-layer deflection plate 11 surrounds a ladder cavity arbitrarily.
Embodiment 5: a kind of integrated fluid reservoir; As shown in Figure 2; Comprise: tank body 10, confession bromine pipeline 8, total return duct 7 and feed pipe 4; An end that supplies bromine pipeline 8 is through the sidewall of tank body 10 and be positioned at tank body 10, and an end of total return duct 7 and feed pipe 4 is through the top of tank body 10 and be positioned at the top of tank body 10 bottoms.Described total return duct 7 is located on the tank body 10 distance and is supplied the nearer side of bromine pipeline 8.
Embodiment 6: a kind of integrated fluid reservoir; Comprise: tank body 10, confession bromine pipeline 8, total return duct 7 and feed pipe 4; An end that supplies bromine pipeline 8 is through the sidewall of tank body 10 and be positioned at tank body 10, and an end of total return duct 7 and feed pipe 4 is through the top of tank body 10 and be positioned at the top of tank body 10 bottoms.Also be provided with deflection plate 11 and base plate 12 in the described tank body 10, an end of base plate 12 is connected near a side that supplies bromine pipeline 8 with tank body 10 bottom surfaces and the angle of base plate 12 and tank body 10 bottom surfaces is 5 °; Deflection plate 11 is located between base plate 12 and the feed pipe 4, and an end of total return duct 7 is through deflection plate 11 and be positioned at the top of base plate 12, and deflection plate 11 is 0 ° with the angle of horizontal plane, and any end of deflection plate 11 is provided with spout hole 9.Described total return duct 7 is located on the tank body 10 distance and is supplied the nearer side of bromine pipeline 8.
Embodiment 7: a kind of integrated fluid reservoir; Comprise: tank body 10, confession bromine pipeline 8, total return duct 7 and feed pipe 4; An end that supplies bromine pipeline 8 is through the sidewall of tank body 10 and be positioned at tank body 10, and an end of total return duct 7 and feed pipe 4 is through the top of tank body 10 and be positioned at the top of tank body 10 bottoms.Also be provided with deflection plate 11 and base plate 12 in the described tank body 10, an end of base plate 12 is connected near a side that supplies bromine pipeline 8 with tank body 10 bottom surfaces and the angle of base plate 12 and tank body 10 bottom surfaces is 5 °; Deflection plate 11 is located between base plate 12 and the feed pipe 4, and an end of total return duct 7 is through deflection plate 11 and be positioned at the top of base plate 12, and deflection plate 11 is 5 ° with the angle of horizontal plane, and deflection plate 11 end nearer apart from horizontal plane is provided with spout hole 9.The quantity of said deflection plate 11 is one deck.
Embodiment 8: the new zinc bromine flow battery that utilizes embodiment 1～6 arbitrary described integrated fluid reservoir to be made into; As shown in Figure 1; Comprise fluid reservoir 1, solution feed pump A2, solution feed pump B3, anodal pipe-line system 41, negative pole pipe-line system 42, pile 5, anodal return duct 71 and negative pole return duct 72; Fluid reservoir 1 is connected with solution feed pump A2, solution feed pump B3, anodal return duct 71 and negative pole return duct 72 respectively; Pile 5 is connected with negative pole return duct 72 with anodal pipe-line system 41, negative pole pipe-line system 42, anodal return duct 71 respectively, and solution feed pump B3 is connected with anodal pipe-line system 41, and solution feed pump A2 is connected with negative pole pipe-line system 42 with anodal pipe-line system 41 respectively.
Embodiment 9: the new zinc bromine flow battery that utilizes embodiment 1～6 arbitrary described integrated fluid reservoir to be made into; As shown in Figure 1; Comprise fluid reservoir 1, solution feed pump A2, solution feed pump B3, anodal pipe-line system 41, negative pole pipe-line system 42, pile 5, anodal return duct 71 and negative pole return duct 72; Fluid reservoir 1 is connected with solution feed pump A2, solution feed pump B3, anodal return duct 71 and negative pole return duct 72 respectively; Pile 5 is connected with negative pole return duct 72 with anodal pipe-line system 41, negative pole pipe-line system 42, anodal return duct 71 respectively, and solution feed pump B3 is connected with anodal pipe-line system 41, and solution feed pump A2 is connected with negative pole pipe-line system 42 with anodal pipe-line system 41 respectively.In the described fluid reservoir 1; An end that supplies bromine pipeline 8 is through the sidewall of tank body 10 and be positioned at tank body 10; The other end is connected with solution feed pump B3, and an end of total return duct 7 is through the top of tank body 10 and be located at the top of tank body 10 bottoms, and the other end is connected with negative pole return duct 72 with anodal return duct 71 respectively; One end of feed pipe 4 is through the top of tank body 10 and be located at the top of tank body 10 bottoms, and the other end is connected with solution feed pump A2.
Embodiment 10: the new zinc bromine flow battery that utilizes embodiment 1～6 arbitrary described integrated fluid reservoir to be made into; As shown in Figure 1; Comprise fluid reservoir 1, solution feed pump A2, solution feed pump B3, anodal pipe-line system 41, negative pole pipe-line system 42, pile 5, anodal return duct 71 and negative pole return duct 72; Fluid reservoir 1 is connected with solution feed pump A2, solution feed pump B3, anodal return duct 71 and negative pole return duct 72 respectively; Pile 5 is connected with negative pole return duct 72 with anodal pipe-line system 41, negative pole pipe-line system 42, anodal return duct 71 respectively, and solution feed pump B3 is connected with anodal pipe-line system 41, and solution feed pump A2 is connected with negative pole pipe-line system 42 with anodal pipe-line system 41 respectively.In the described fluid reservoir 1; An end that supplies bromine pipeline 8 is through the sidewall of tank body 10 and be positioned at tank body 10; The other end is connected with solution feed pump B3, and an end of total return duct 7 is through the top of tank body 10 and be located at the top of tank body 10 bottoms, and the other end is connected with negative pole return duct 72 with anodal return duct 71 respectively; One end of feed pipe 4 is through the top of tank body 10 and be located at the top of tank body 10 bottoms, and the other end is connected with solution feed pump A2.Also comprise: heat-exchange system, described heat-exchange system comprises: heat exchanger 61 and cooler 62, cooler 62 is connected with heat exchanger 61, and heat exchanger 61 is connected with anodal return duct 71.
Embodiment 11: a kind of integrated fluid reservoir; As shown in Figure 2; Comprise: tank body 10, confession bromine pipeline 8, total return duct 7 and feed pipe 4; An end that supplies bromine pipeline 8 is through the sidewall of tank body 10 and be positioned at tank body 10, and an end of total return duct 7 and feed pipe 4 is through the top of tank body 10 and be positioned at the top of tank body 10 bottoms.Also be provided with deflection plate 11 and base plate 12 (as shown in Figure 3) in the described tank body 10, an end of base plate 12 is connected near a side that supplies bromine pipeline 8 with tank body 10 bottom surfaces and the angle of base plate 12 and tank body 10 bottom surfaces is 5 °; Deflection plate 11 is located between base plate 12 and the feed pipe 4; One end of total return duct 7 is through deflection plate 11 and be positioned at the top of base plate 12; Deflection plate 11 is 5 ° with the angle of horizontal plane, and deflection plate 11 end nearer apart from horizontal plane is provided with spout hole 9 (as shown in Figure 4).The quantity of said deflection plate 11 is two-layer, and two-layer deflection plate 11 surrounds a ladder cavity.Described spout hole 9 both sides also are provided with magnetic material (as shown in Figure 5).Described total return duct 7 is located on the tank body 10 distance and is supplied the nearer side of bromine pipeline 8.
The new zinc bromine flow battery that utilizes above-mentioned integrated fluid reservoir to be made into; As shown in Figure 1; Comprise fluid reservoir 1, solution feed pump A2, solution feed pump B3, anodal pipe-line system 41, negative pole pipe-line system 42, pile 5, anodal return duct 71 and negative pole return duct 72; Fluid reservoir 1 is connected with solution feed pump A2, solution feed pump B3, anodal return duct 71 and negative pole return duct 72 respectively; Pile 5 is connected with negative pole return duct 72 with anodal pipe-line system 41, negative pole pipe-line system 42, anodal return duct 71 respectively, and solution feed pump B3 is connected with anodal pipe-line system 41, and solution feed pump A2 is connected with negative pole pipe-line system 42 with anodal pipe-line system 41 respectively.In the described fluid reservoir 1; An end that supplies bromine pipeline 8 is through the sidewall of tank body 10 and be positioned at tank body 10; The other end is connected with solution feed pump B3, and an end of total return duct 7 is through the top of tank body 10 and be located at the top of tank body 10 bottoms, and the other end is connected with negative pole return duct 72 with anodal return duct 71 respectively; One end of feed pipe 4 is through the top of tank body 10 and be located at the top of tank body 10 bottoms, and the other end is connected with solution feed pump A2.Also comprise: heat-exchange system, described heat-exchange system comprises: heat exchanger 61 and cooler 62, cooler 62 is connected with heat exchanger 61, and heat exchanger 61 is connected with fluid reservoir 1.
Among the foregoing description 10 and the embodiment 11, described heat-exchange system comprises: heat exchanger 61 and cooler 62, and cooler 62 is connected with heat exchanger 61, and heat exchanger 61 can also be connected with negative pole return duct 72.
The operation principle of a kind of embodiment of the present invention: zinc bromine flow battery is when work, and both positive and negative polarity in the reaction that electrode surface takes place is respectively:
Anodal: Br
2+ 2e
-→ 2Br
-
Negative pole: Zn-2e
-→ Zn
2+
Overall reaction: Zn+Br
2→ Zn
2++ 2Br
-
In operation process, in the electrolyte that should guarantee to extract out by feed pipe 4, Br
2Concentration minimum.Influence three factors that have of bromine concentration:
1, is dissolved in the middle mutually Br of electrolyte clear liquid
2
2, be suspended in the bromo-complex of electrolyte clear liquid in mutually owing to flow
3、Br
3 -。
In system, exist reaction:
This reaction
therefore can spontaneously be carried out at normal temperatures.
Because Br
2Solubility in water is less, and bromo-complex is with mutually immiscible with clear liquid, and with clear liquid bigger density contrast is arranged mutually, and is therefore limited to the influence of self discharge.Br
3 -Being that form with ion is present in the middle of the electrolyte, having fine solubility, therefore, is one of major reason that causes the self discharge of zinc bromine flow battery.As shown in Figure 6, change Br with battery charge state
3 -Ion concentration is shown in curve, at 25 ℃ of following 2.5M ZnBr
2In the electrolyte, in battery charge and discharge process, Br
3 -Ion concentration can reach 1.4mol/L, the Br of high concentration
3 -Ion gets into negative pole, will cause corrosion by anticathode surface zinc sedimentary deposit, thereby cause more serious self discharge.
Shown in Figure 1 is the structural representation of zinc bromine flow battery in this programme, and its operation principle is that electrolyte is pumped from liquid storage pipe 1 by solution feed pump A2; Branch flows into positive electrical and separates liquid pipeline system 41 and negative pole electrolysis liquid pipeline system 42; Get into the both positive and negative polarity of pile 5 then respectively, after the generation electrochemical reaction, flow out from anodal return duct 71 and negative pole return duct 72 respectively; Gather to total return duct 7, return fluid reservoir 5.Heat-exchange system is arranged in the system, comprise heat exchanger 61 and cooler 62, institute's mark is changed to the heat exchange of negative pole electrolyte among Fig. 1, and is same, and heat-exchange system can be installed in anodal pipe-line system 71 places, or directly gives fluid reservoir 1 heat exchange.Structure that Fig. 1 marks is the typical flow battery structure of the present invention, and all the sensors and control section do not mark.
Fig. 2, Fig. 3 are the structural representation of fluid reservoir 1, comprise tank body 10, confession bromine pipeline 8, total return duct 7 and feed pipe 4, also are provided with deflection plate 11 and base plate 12 in the tank body 10, and an end nearer apart from tank body 10 bottoms of deflection plate 11 also is provided with spout hole 9.Electrolyte in liquid storage pipe 1 inner operation principle is: electrolyte is extracted out from feed pipe 4, gets into solution feed pump A2, after the completion circulation, gets back to fluid reservoir 1 by total return duct 7.Bromo-complex in the pipeline and is back to along base plate 12 clinoplains and supplies near bromine pipeline 8 inlets because self density is settled down near the base plate 12.Clear liquid phase in other electrolyte (containing the small amount of bromine complex compound) is compensated by 9 pairs of upper strata electrolyte of spout hole.In flow process, part not by the bromo-complex of sorting continue from clear liquid mutually separation, and be back to the orlop of fluid reservoir 1 along the inclined-plane of deflection plate 11.Be bromo-complex enrichment region supplying near the bromine pipeline 8 this moment.During charging, attonity; During discharge, bromo-complex gets into anodal electrolysis liquid pipeline system 41 because the effect of solution feed pump B3 is drawn out of from supplying bromine pipeline 8.
At overfall 9 places, magnetic material is installed, described magnetic material is general permanent magnet, like magnet; Its magnetic field intensity is smaller or equal to 1T, and is as shown in Figure 5, for convenient statement, as shown in Figure 2; The horizontal long side direction of definition fluid reservoir is a directions X, and height is the Y direction, and the horizontal short direction is the Z direction.At spout hole 9 places, N represents the arctic, magnetic field, and S represents the South Pole, magnetic field, and magnetic line of force direction is the Z direction.
Under the effect of charged ion, when moving through spout hole 9, under the effect of magnetic field B, receive size and be the active force of F with speed v in electrolyte flow.Set forth for convenient, the definition speed v has corresponding velocity component v
X, v
Y, v
Z, the corresponding F of corresponding existence
X, F
Y, F
Z, direction and v
X, v
Y, v
ZVertically.Definition magnetic field is the simplification problem in the X-Z plane, suppose that this magnetic field is uniform magnetic field, and magnetic field intensity is B, along Z axle (or negative) direction just.Then have:
F
X＝qv
xB
F
Y＝qv
YB
F
Z＝0
Ion is stressed in magnetic field, and the direction of motion of its original ion changes, thereby has improved Br
3 -The ion residence time at the volley, improved the effect of gravity separation.
Claims (10)
1. integrated fluid reservoir; It is characterized in that; Comprise: tank body (10), confession bromine pipeline (8), total return duct (7) and feed pipe (4); An end that supplies bromine pipeline (8) is through the sidewall of tank body (10) and be positioned at tank body (10), and an end of total return duct (7) and feed pipe (4) is through the top of tank body (10) and be positioned at the top bottom the tank body (10).
2. integrated fluid reservoir according to claim 1; It is characterized in that; Also be provided with deflection plate (11) and base plate (12) in the described tank body (10), an end of base plate (12) is connected near a side that supplies bromine pipeline (8) with tank body (10) bottom surface and the angle of base plate (12) and tank body (10) bottom surface is 5 °～10 °; Deflection plate (11) is located between base plate (12) and the feed pipe (4); One end of total return duct (7) is through deflection plate (11) and be positioned at the top of base plate (12); Deflection plate (11) is 0 °～30 ° with the angle of horizontal plane, and deflection plate (a 11) end nearer apart from horizontal plane is provided with spout hole (9).
3. integrated fluid reservoir according to claim 2 is characterized in that, described deflection plate (11) is 5 ° with the angle of horizontal plane, and base plate (12) is 5 ° with the angle of tank body (10) bottom surface.
4. according to claim 2 or 3 described integrated fluid reservoirs, it is characterized in that the quantity of said deflection plate (11) is one deck at least, when the quantity of deflection plate (11) during greater than one deck, adjacent two-layer deflection plate (11) surrounds a ladder cavity arbitrarily.
5. according to claim 2 or 3 described integrated fluid reservoirs, it is characterized in that described spout hole (9) both sides also are provided with magnetic material.
6. according to claim 1,2,3 or 5 described integrated fluid reservoirs, it is characterized in that described total return duct (7) is located at tank body (10) and is gone up the nearer side of distance confession bromine pipeline (8).
7. the new zinc bromine flow battery that utilizes the arbitrary described integrated fluid reservoir of claim 1～6 to be made into; It is characterized in that; Comprise fluid reservoir (1), solution feed pump A (2), solution feed pump B (3), anodal pipe-line system (41), negative pole pipe-line system (42), pile (5), anodal return duct (71) and negative pole return duct (72); Fluid reservoir (1) is connected with solution feed pump A (2), solution feed pump B (3), anodal return duct (71) and negative pole return duct (72) respectively; Pile (5) is connected with anodal pipe-line system (41), negative pole pipe-line system (42), anodal return duct (71) and negative pole return duct (72) respectively; Solution feed pump B (3) is connected with anodal pipe-line system (41), and solution feed pump A (2) is connected with negative pole pipe-line system (42) with anodal pipe-line system (41) respectively.
8. new zinc bromine flow battery according to claim 7; It is characterized in that; In the described fluid reservoir (1), an end that supplies bromine pipeline (8) is through the sidewall of tank body (10) and be positioned at tank body (10), and the other end is connected with solution feed pump B (3); One end of total return duct (7) is through the top of tank body (10) and be located at the top of tank body (10) bottom; The other end is connected with negative pole return duct (72) with anodal return duct (71) respectively, and an end of feed pipe (4) is through the top of tank body (10) and be located at the top of tank body (10) bottom, and the other end is connected with solution feed pump A (2).
9. according to claim 7 or 8 described new zinc bromine flow batteries; It is characterized in that; Also comprise: heat-exchange system; Described heat-exchange system comprises: heat exchanger (61) and cooler (62), and cooler (62) is connected with heat exchanger (61), and heat exchanger (61) is connected with anodal return duct (71), negative pole return duct (72) or fluid reservoir (1).
10. new zinc bromine flow battery according to claim 9 is characterized in that, described cooler (62) is connected with heat exchanger (61), and heat exchanger (61) is connected with fluid reservoir (1).
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| CN105680082A (en) * | 2014-11-17 | 2016-06-15 | 中国科学院大连化学物理研究所 | Long-lifetime zinc-bromine flow battery structure and electrolyte |
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| CN105308771A (en) * | 2013-03-08 | 2016-02-03 | 普里默斯电力公司 | Reservoir for multiphase electrolyte flow control |
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| CN107845826B (en) * | 2016-09-21 | 2023-08-11 | 中国科学院大连化学物理研究所 | Zinc bromine single flow battery |
| CN107887566A (en) * | 2016-09-30 | 2018-04-06 | 北京好风光储能技术有限公司 | A kind of drive control method of lithium ion flow battery system |
| CN107887566B (en) * | 2016-09-30 | 2020-08-04 | 北京好风光储能技术有限公司 | Drive control method of lithium ion flow battery system |
| CN106910918A (en) * | 2017-03-31 | 2017-06-30 | 湖南省德沃普储能有限公司 | Flow battery energy storage mixes liquid system and its control method |
| CN109860658A (en) * | 2017-11-28 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of restoration methods of zinc bromine single flow battery performance |
| CN109860658B (en) * | 2017-11-28 | 2022-02-22 | 中国科学院大连化学物理研究所 | Method for recovering performance of zinc-bromine single flow battery |
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