CN104143651A - Redox flow cell system - Google Patents
Redox flow cell system Download PDFInfo
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- CN104143651A CN104143651A CN201310169708.5A CN201310169708A CN104143651A CN 104143651 A CN104143651 A CN 104143651A CN 201310169708 A CN201310169708 A CN 201310169708A CN 104143651 A CN104143651 A CN 104143651A
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- pile
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a redox flow cell system. The redox flow cell system comprises a cationic membrane pile, an anionic membrane pile, a positive electrode circulating pump, a positive electrode pipeline, a negative electrode circulating pump, a negative electrode pipeline, a positive electrode electrolyte storage tank filled with an electrolyte, and a negative electrode electrolyte storage tank filled with an electrolyte. The redox flow cell system formed by simultaneously using the cationic membrane pile and the anionic membrane pile can effectively reduce the change of the concentrations and the volumes of positive electrode and negative electrode electrolyte solutions in order to improve the efficiency of the cell system during long-term charge and discharge circulation and the utilization rates of the electrolyte solutions and prolong the service lives of the electrolyte solutions of the cell system. The system saves the cell maintenance time, avoids the consumption of extra electric energy and manpower and reduces the maintenance cost.
Description
Technical field
The present invention relates to a kind of redox flow battery system.
Background technology
Along with the continuous exploitation of global non-regeneration energy, cause huge lack of energy and the problem of environmental pollution, for link and this significant problem of solution energy crisis, the exploitation of regenerative resource and use are extremely urgent.The large-scale development stage that enters of the regenerative resources such as current wind energy, solar energy, still due to the unsteadiness of the regenerative resource such as wind energy, solar energy, electrical network is caused to huge impact, have a strong impact on the stable operation of electrical network.Therefore, the jumbo energy-storage system of research and development high efficiency, low cost, high stability is by renewable energy storages such as unsettled wind energy, solar energy, and then stable supply electrical network, stablizes electrical network output.In numerous energy-storage systems, redox flow battery system has battery and capacity independent design, without solid phase reaction, low price, high stability, high reliability, the advantage such as maintenance is simple, maintenance cost is low, so in recent years, redox flow batteries had obtained swift and violent development.
In redox flow batteries, vanadium redox battery (Vanadium Redox Flow Battery) has obtained more concern, because its vanadium ion form with different valence state is present in sulfuric acid solution, by external pump, vanadium ion sulfuric acid solution is pressed in battery, and in each half-cell, forms the closed-loop path of circulation.Between positive and negative half-cell, separate by amberplex, vanadium ion sulfuric acid solution concurrent flow is crossed electrode, collects and conduction current, and then make the chemical energy being stored in vanadium ion sulfuric acid solution be converted into electric energy by double electrode plate.
The battery of tradition composition redox flow battery system is in assembling process, general adopt the amberplex of two types as the barrier film of pile: wherein one is cation-exchange membrane, this film carries out after long-term charge and discharge cycles at battery, the volume of the electrolyte solution of system can move to positive pole from negative pole, and the concentration of positive and negative electrode electrolyte solution also can produce certain variation; Another is anion-exchange membrane, and this film carries out after long-term charge and discharge cycles at battery, and the volume of the electrolyte solution of system can move to negative pole from positive pole, and the concentration of positive and negative electrode electrolyte solution also can produce certain variation; So be the migration that any single amberplex all can not stop ion and water completely, cause concentration and the volume of positive and negative electrode solution all can occur a certain distance, this also serious impact the efficiency of battery system and the utilance of electrolyte solution.
In order to address this problem, traditional way need to be after battery system charge and discharge cycles a period of time mostly, and mixed positive and negative electrode electrolyte solution, makes the electrolyte solution of system return to the initial state that approaches mutually.This process is not only more loaded down with trivial details, and will consume extra electric energy and manpower.
Summary of the invention
The object of the invention is to solve the positive and negative electrode concentration of electrolyte solutions brought due to the long-term charge and discharge cycles of battery system and the variation of volume, improve the efficiency of battery and the utilance of electrolyte solution, also reduce as much as possible because mutually mixed positive and negative electrode electrolyte solution consumes extra electric energy and manpower simultaneously.
For achieving the above object, the present invention adopts following concrete technical scheme,
A kind of redox flow battery system, comprises by cationic membrane pile, anionic membrane pile, anodal circulating pump, anodal pipeline, negative pole circulating pump, negative pole pipeline, is filled with the anode electrolyte storage tank of electrolyte and is filled with the negative pole electrolysis liquid storage tank of electrolyte;
Electrolyte in anode electrolyte storage tank is connected with the anodal entrance and exit of cationic membrane pile and anionic membrane pile by anodal pipeline through anodal circulating pump;
Electrolyte in negative pole electrolysis liquid storage tank is connected with the negative pole entrance and exit of cationic membrane pile and anionic membrane pile by negative pole pipeline through negative pole circulating pump.
Described cationic membrane pile is in series by 2 monocells that adopt above ionic membrane to make barrier film; Described anionic membrane pile is in series by 2 monocells that adopt above anionic membrane to make barrier film.
In pile, monocell joint number is 2～100.
Described battery system comprises cationic membrane pile and anionic membrane pile, and wherein cationic membrane pile quantity and anionic membrane pile quantity are respectively m and n, 1≤m≤1000,1≤n≤1000.
In described battery system, between cationic membrane pile and anionic membrane pile, Ye road or circuit are that series, parallel or string series-parallel connection mode combine.
The electrode area of pile single battery is at 200～10000cm
2between.
The cationic membrane pile of composition flow battery system used and the arrangement mode of anionic membrane pile are not limit, in the time of this class battery system of composition, can first use cationic membrane pile assembled battery system forward part, and then with anionic membrane pile assembled battery system rear section; Can first use anionic membrane pile assembled battery system forward part, and then with cationic membrane pile assembled battery system rear section; Also can be the assembling that use cationic membrane pile alternately and anionic membrane pile (or anionic membrane pile and cationic membrane pile) have removed battery system; More can first use partial cation film pile assembled battery system and then use anionic part film battery assembled battery system, and then repeat this process and complete the assembling of whole battery system; Can also first use anionic part film pile assembled battery system and then use partial cation film pile assembled battery system, and then repeat this process and complete the assembling of whole battery system.
The reasonable control of the quantity ratio by the cationic membrane pile to used and anionic membrane pile, because electrolyte solution is in cationic membrane pile and the different characteristic of migratory direction, speed in anionic membrane pile, and then reduce the volume of system positive and negative electrode electrolyte solution and the difference of concentration, and then improve the efficiency of redox flow battery system in the time carrying out long-term charge and discharge cycles and the utilance of electrolyte solution.Preferably composition redox flow battery system cationic membrane pile used quantity and anionic membrane pile quantity ratio used are between 1/100～100/1; More preferably the ratio that forms redox flow battery system cationic membrane pile used quantity and anionic membrane pile quantity used is between 1/50～50/1; The ratio that preferably forms again redox flow battery system cationic membrane pile used quantity and anionic membrane pile quantity used is between 1/20～20/1; The ratio that most preferably forms redox flow battery system cationic membrane pile used quantity and anionic membrane pile quantity used is between 1/10～10/1.
Can be Nafion115, Nafion117, Nafion212 etc. or other cationic membrane that DuPont company produces for the cationic membrane of assembling pile, can be the VX20 film that produces of fumatech company etc. or other anionic membrane for assembling the anionic membrane of pile.
Beneficial effect:
1. the present invention is by form redox flow battery system with cationic membrane pile and anionic membrane pile simultaneously, utilize electrolyte solution migratory direction, principle that migration velocity is different in the pile of two kinds of films, can effectively reduce the variation of positive and negative electrode concentration of electrolyte solutions and volume, and then improve the efficiency of battery system in the time carrying out long-term charge and discharge cycles and the utilance of electrolyte solution, extend the useful life of battery system electrolyte solution.
2. the present invention can replace at redox flow battery system and carrying out after the charge and discharge cycles regular hour, and mixed positive and negative electrode electrolyte solution mutually returns to electrolyte solution to approach the way of initial conditions.Can save preventive maintenance time, avoid consuming extra electric energy and manpower, reduce maintenance cost.
Brief description of the drawings
Fig. 1 is the vanadium redox battery system schematic block diagram that embodiment 1 assembles;
Fig. 2 is the vanadium redox battery system schematic block diagram that embodiment 2 assembles;
Fig. 3 is the vanadium redox battery system schematic block diagram that embodiment 3 assembles;
Fig. 4 is traditional vanadium redox battery system that comparative example 1 and comparative example 2 are assembled, this system is made up of 4 piles, and the pile that wherein forms this vanadium redox battery system is all cationic membrane pile or is all anionic membrane pile schematic block diagram;
Fig. 5 is traditional vanadium redox battery system that comparative example 3 and comparative example 4 are assembled, this system is made up of 8 piles, and the pile that wherein forms this vanadium redox battery system is all cationic membrane pile or is all anionic membrane pile schematic block diagram.
Embodiment
As an example of vanadium redox battery system example, the present invention is described in further detail below, but the present invention is not limited only to this.
Embodiment 1
Tested vanadium redox battery system is made up of 4 piles, the cationic membrane pile and the anionic membrane pile quantity ratio that wherein form this vanadium redox battery system are 1/3, each this pile monocell joint number is 5 joints, the cationic membrane pile of this vanadium redox battery system of composition used and the arrangement mode of anionic membrane pile are not limit, and the present embodiment forms the cationic membrane pile of this vanadium redox battery system and the arrangement mode of anionic membrane pile as shown in Figure 1.This system is made up of 4 piles, the cationic membrane pile and the anionic membrane pile quantity ratio that wherein form this vanadium redox battery system are 1/3, the cationic membrane and the anionic membrane that wherein form this vanadium redox battery system can be arranged in any way, just a kind of arrangement mode wherein of this figure.
Embodiment 2
Tested vanadium redox battery system is made up of 4 piles, the cationic membrane pile and the anionic membrane pile quantity ratio that wherein form this vanadium redox battery system are 2/2, each this pile monocell joint number is 5 joints, the cationic membrane pile of this vanadium redox battery system of composition used and the arrangement mode of anionic membrane pile are not limit, and the present embodiment forms the cationic membrane pile of this vanadium redox battery system and the arrangement mode of anionic membrane pile as shown in Figure 2.
Embodiment 3
Tested vanadium redox battery system is made up of 4 piles, the cationic membrane pile and the anionic membrane pile quantity ratio that wherein form this vanadium redox battery system are 3/1, each this pile monocell joint number is 5 joints, the cationic membrane pile of this vanadium redox battery system of composition used and the arrangement mode of anionic membrane pile are not limit, and the present embodiment forms the cationic membrane pile of this vanadium redox battery system and the arrangement mode of anionic membrane pile as shown in Figure 3.
Embodiment 4
Tested vanadium redox battery system is made up of 8 piles, the cationic membrane pile and the anionic membrane pile quantity ratio that wherein form this vanadium redox battery system are 1/7, each this pile monocell joint number is 5 joints, and the cationic membrane pile of this vanadium redox battery system of composition used and the arrangement mode of anionic membrane pile are not limit.
Embodiment 5
Tested vanadium redox battery system is made up of 8 piles, the cationic membrane pile and the anionic membrane pile quantity ratio that wherein form this vanadium redox battery system are 2/6, each this pile monocell joint number is 5 joints, and the cationic membrane pile of this vanadium redox battery system of composition used and the arrangement mode of anionic membrane pile are not limit.
Embodiment 6
Tested vanadium redox battery system is made up of 8 piles, the cationic membrane pile and the anionic membrane pile quantity ratio that wherein form this vanadium redox battery system are 3/5, each this pile monocell joint number is 5 joints, and the cationic membrane pile of this vanadium redox battery system of composition used and the arrangement mode of anionic membrane pile are not limit.
Embodiment 7
Tested vanadium redox battery system is made up of 8 piles, the cationic membrane pile and the anionic membrane pile quantity ratio that wherein form this vanadium redox battery system are 4/4, each this pile monocell joint number is 5 joints, and the cationic membrane pile of this vanadium redox battery system of composition used and the arrangement mode of anionic membrane pile are not limit.
Embodiment 8
Tested vanadium redox battery system is made up of 8 piles, the cationic membrane pile and the anionic membrane pile quantity ratio that wherein form this vanadium redox battery system are 5/3, each this pile monocell joint number is 5 joints, and the cationic membrane pile of this vanadium redox battery system of composition used and the arrangement mode of anionic membrane pile are not limit.
Embodiment 9
Tested vanadium redox battery system is made up of 8 piles, the cationic membrane pile and the anionic membrane pile quantity ratio that wherein form this vanadium redox battery system are 6/2, each this pile monocell joint number is 5 joints, and the cationic membrane pile of this vanadium redox battery system of composition used and the arrangement mode of anionic membrane pile are not limit.
Embodiment 10
Tested vanadium redox battery system is made up of 8 piles, the cationic membrane pile and the anionic membrane pile quantity ratio that wherein form this vanadium redox battery system are 7/1, each this pile monocell joint number is 5 joints, and the cationic membrane pile of this vanadium redox battery system of composition used and the arrangement mode of anionic membrane pile are not limit.
Comparative example 1
Tested vanadium redox battery system is made up of 4 piles, and the pile that wherein forms this vanadium redox battery system is all cationic membrane pile, and each pile monocell joint number is 5 joints; Pile monocell response area is 800cm
2, vanadium concentration of electrolyte solutions is 1.5mol/L, the current density of battery constant current charging-discharging is 80mA/cm
2, single battery discharges and recharges cut-off battery and is respectively 1.55V and 1.0V, and the initial liquid tank level height of both positive and negative polarity is 200cm.
Comparative example 2
Tested vanadium redox battery system is made up of 4 piles, and the pile that wherein forms this vanadium redox battery system is all anionic membrane pile, and each pile monocell joint number is 5 joints; Pile monocell response area is 800cm
2, vanadium concentration of electrolyte solutions is 1.5mol/L, the current density of battery constant current charging-discharging is 80mA/cm
2, single battery discharges and recharges cut-off battery and is respectively 1.55V and 1.0V, and the initial liquid tank level height of both positive and negative polarity is 200cm.
Comparative example 3
Tested vanadium redox battery system is made up of 8 piles, and the pile that wherein forms this vanadium redox battery system is all cationic membrane pile, and each pile monocell joint number is 5 joints; Pile monocell response area is 800cm
2, vanadium concentration of electrolyte solutions is 1.5mol/L, the current density of battery constant current charging-discharging is 80mA/cm
2, single battery discharges and recharges cut-off battery and is respectively 1.55V and 1.0V, and the initial liquid tank level height of both positive and negative polarity is 400cm.
Comparative example 4
Tested vanadium redox battery system is made up of 8 piles, and the pile that wherein forms this vanadium redox battery system is all anionic membrane pile, and each pile monocell joint number is 5 joints; Pile monocell response area is 800cm
2, vanadium concentration of electrolyte solutions is 1.5mol/L, the current density of battery constant current charging-discharging is 80mA/cm
2, single battery discharges and recharges cut-off battery and is respectively 1.55V and 1.0V, and the initial liquid tank level height of both positive and negative polarity is 400cm.
Illustrate:
In embodiment 1～embodiment 3 and comparative example 1～comparative example 2: the monocell response area that wherein forms the pile of this vanadium redox battery system is all 800cm
2; Single battery discharges and recharges cut-off battery and is respectively 1.55V and 1.0V; The current density of battery constant current charging-discharging is 80mA/cm
2; Vanadium concentration of electrolyte solutions is all 1.5mol/L; The initial liquid tank level height of both positive and negative polarity is 200cm; Cationic membrane used is all Nafion115 film; Anionic membrane used is all VX20 film;
In embodiment 4～embodiment 10 and comparative example 3～comparative example 4: the monocell response area that wherein forms the pile of this vanadium redox battery system is all 800cm
2; Single battery discharges and recharges cut-off battery and is respectively 1.55V and 1.0V; The current density of battery constant current charging-discharging is 80mA/cm
2; Vanadium concentration of electrolyte solutions is all 1.5mol/L; The initial liquid tank level height of both positive and negative polarity is 400cm; Cationic membrane used is all Nafion115 film; Anionic membrane used is all VX20 film.
Test:
Adopt the energy efficiency (EE) of Arbin BT-2000 battery charging and discharging instrument (manufacture of Arbin company of the U.S.) test battery system; Adopt ruler to measure the liquid level of both positive and negative polarity electrolyte storage tank; Test result as shown in Table 1.
Table one
As can be seen from the above table, redox flow battery system according to the present invention is after through 100 charge and discharge cycles: 1. the energy efficiency of redox flow battery system all remains on more than 79%, and the utilance of electrolyte solution also exceedes 69%; 2. the liquid level difference of the positive and negative electrode electrolyte solution fluid reservoir of redox flow battery system is effectively alleviated, owing to using in cationic membrane pile in redox flow battery system and anionic membrane pile, play the left and right of balance both positive and negative polarity ion concentration, and then be more conducive to improve the utilance of whole electrolyte solution.And wherein form cationic membrane pile and the anionic membrane pile quantity ratio of redox flow battery system by reasonable arrangement, in the time of long-time, many circular flow, the energy efficiency of battery system and the utilance of electrolyte solution can exceed the energy efficiency of traditional redox flow battery system and the utilance of electrolyte solution.
By contrast, in the time only using same cationic membrane pile or anionic membrane pile composition redox flow battery system, after through 100 charge and discharge cycles, the liquid level difference of the positive and negative electrode electrolyte solution fluid reservoir of redox flow battery system is very large, and the utilance of electrolyte solution is also lower than 63%.
Claims (5)
1. a redox flow battery system, comprises by cationic membrane pile, anionic membrane pile, anodal circulating pump, anodal pipeline, negative pole circulating pump, negative pole pipeline, is filled with the anode electrolyte storage tank of electrolyte and is filled with the negative pole electrolysis liquid storage tank of electrolyte;
Electrolyte in anode electrolyte storage tank is connected with the anodal entrance and exit of cationic membrane pile and anionic membrane pile by anodal pipeline, and the anodal pipeline between anodal entrance and electrolyte storage tank is provided with anodal circulating pump;
Electrolyte in negative pole electrolysis liquid storage tank is connected with the negative pole entrance and exit of cationic membrane pile and anionic membrane pile by negative pole pipeline, and the negative pole pipeline between negative pole entrance and electrolyte storage tank is provided with negative pole circulating pump.
2. redox flow battery system according to claim 1, is characterized in that: described cationic membrane pile is in series by 2 monocells that adopt above cationic membrane to make barrier film; Described anionic membrane pile is in series by 2 monocells that adopt above anionic membrane to make barrier film.
3. redox flow battery system according to claim 2, is characterized in that: in pile, monocell joint number is 2～100.
4. redox flow battery system according to claim 1, it is characterized in that: described battery system comprises cationic membrane pile and anionic membrane pile, wherein cationic membrane pile quantity and anionic membrane pile quantity are respectively m and n, 1≤m≤1000,1≤n≤1000.
5. redox flow battery system according to claim 1, is characterized in that: in described battery system, between cationic membrane pile and anionic membrane pile, Ye road or circuit are that series, parallel or string series-parallel connection mode combine.
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| CN201310169708.5A CN104143651A (en) | 2013-05-09 | 2013-05-09 | Redox flow cell system |
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| CN201310169708.5A CN104143651A (en) | 2013-05-09 | 2013-05-09 | Redox flow cell system |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106169586A (en) * | 2016-08-12 | 2016-11-30 | 洁能电投（北京）新能源科技有限公司 | A kind of flow battery system and the preparation method of positive electrode thereof |
| CN107256977A (en) * | 2017-06-29 | 2017-10-17 | 江苏科技大学 | One kind is based on unilateral feed flow modularization zinc-nickel list liquid energy-storage system |
| CN109923719A (en) * | 2016-12-19 | 2019-06-21 | 昭和电工株式会社 | The operation method of redox flow batteries |
| CN110845849A (en) * | 2018-08-21 | 2020-02-28 | 北京普能世纪科技有限公司 | Non-crosslinked anion exchange membrane and preparation method thereof, and all-vanadium redox flow battery |
| US10763532B2 (en) | 2016-10-13 | 2020-09-01 | Lg Chem, Ltd. | Electrolyte storage unit for redox flow battery and vanadium redox flow battery comprising same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1284208A (en) * | 1998-01-28 | 2001-02-14 | 凯米科有限责任公司 | Rebox flow battery system and cell stack |
| CN102055000A (en) * | 2009-10-29 | 2011-05-11 | 北京普能世纪科技有限公司 | Redox flow battery and method for enabling battery to operate continuously for long time |
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2013
- 2013-05-09 CN CN201310169708.5A patent/CN104143651A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1284208A (en) * | 1998-01-28 | 2001-02-14 | 凯米科有限责任公司 | Rebox flow battery system and cell stack |
| CN102055000A (en) * | 2009-10-29 | 2011-05-11 | 北京普能世纪科技有限公司 | Redox flow battery and method for enabling battery to operate continuously for long time |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106169586A (en) * | 2016-08-12 | 2016-11-30 | 洁能电投（北京）新能源科技有限公司 | A kind of flow battery system and the preparation method of positive electrode thereof |
| US10763532B2 (en) | 2016-10-13 | 2020-09-01 | Lg Chem, Ltd. | Electrolyte storage unit for redox flow battery and vanadium redox flow battery comprising same |
| CN109923719A (en) * | 2016-12-19 | 2019-06-21 | 昭和电工株式会社 | The operation method of redox flow batteries |
| CN107256977A (en) * | 2017-06-29 | 2017-10-17 | 江苏科技大学 | One kind is based on unilateral feed flow modularization zinc-nickel list liquid energy-storage system |
| CN110845849A (en) * | 2018-08-21 | 2020-02-28 | 北京普能世纪科技有限公司 | Non-crosslinked anion exchange membrane and preparation method thereof, and all-vanadium redox flow battery |
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Application publication date: 20141112 |