CN104518228A - All-vanadium oxidation reduction flow battery adjusting method - Google Patents
All-vanadium oxidation reduction flow battery adjusting method Download PDFInfo
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- CN104518228A CN104518228A CN201310454929.7A CN201310454929A CN104518228A CN 104518228 A CN104518228 A CN 104518228A CN 201310454929 A CN201310454929 A CN 201310454929A CN 104518228 A CN104518228 A CN 104518228A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04298—Processes for controlling fuel cells or fuel cell systems
- H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
- H01M8/04791—Concentration; Density
- H01M8/0482—Concentration; Density of the electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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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
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Abstract
The present invention relates to an all-vanadium oxidation reduction flow battery adjusting method. According to the all-vanadium oxidation reduction flow battery adjusting method, equipment comprises a battery separation membrane, a positive electrode electrolyte storage tank and a negative electrode electrolyte storage tank; when the battery separation membrane is a cation exchange membrane, before the battery runs, the volume ratio of the positive electrode electrolyte added to the positive electrode electrolyte storage tank to the negative electrode electrolyte added to the negative electrode electrolyte storage tank is 1/1.2-1/5; or when the battery separation membrane is an anion exchange membrane, before the battery runs, the volume ratio of the positive electrode electrolyte added to the positive electrode electrolyte storage tank to the negative electrode electrolyte added to the negative electrode electrolyte storage tank is 5/1-1.5/1. With the adjusting method of the present invention, when the battery runs for a long time, the electrolyte utilization rate of the battery can be effectively improved, the batter cost can be reduced, and the battery efficiency can be improved.
Description
Technical field
The present invention relates to a kind of flow battery, more specifically, the invention provides a kind of can, method that multi cycle when running improve its energy content of battery efficiency and electrolyte utilance long-time at flow battery system.
Background technology
Along with the continuous exploitation of global non-regeneration energy, caused the problem of huge lack of energy and environmental pollution, in order to link and this significant problem of solution energy crisis, exploitation and the use of regenerative resource are extremely urgent.The large-scale development stage that enters of the regenerative resources such as current wind energy, solar energy, but due to the unsteadiness of the regenerative resource such as wind energy, solar energy, huge impact is caused to electrical network, has 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 the wind energy of instability, solar energy, and then stable supply electrical network, stablizes electrical network and export.
In numerous energy-storage systems, the advantages such as redox flow battery energy storage system has battery and capacity independent design, Solid Free react, low price, high stability, high reliability, maintenance is simple, maintenance cost is low, so in recent years, redox flow batteries obtained swift and violent development.
But due to flow battery in actual applications, because positive and negative electrode electrolyte can not separate by battery diaphragm completely.Therefore, when battery long-time running, the transport phenomena of electrolyte is also just unavoidable.Under normal circumstances, when adopting cationic membrane as battery diaphragm, electrolyte moves the positive pole to battery from the negative pole of battery; When adopting anionic membrane as battery diaphragm, electrolyte then can move negative pole to battery from the positive pole of battery.Just because of the impact of transport phenomena, cause the amount of both positive and negative polarity electrolyte species unbalance, finally impel battery in long-time running, produce larger capacity attenuation, the utilance of electrolyte also significantly declines; Simultaneously due to the migration of positive and negative electrode electrolyte, the positive and negative electrode concentration of electrolyte caused produces deviation, thus increases concentration polarization, and reduces the efficiency of battery due to the increase of concentration polarization.
In order to address this problem, mostly traditional way needed after battery system charge and discharge cycles a period of time, and mixed positive and negative electrode electrolyte solution, makes the electrolyte solution of system return to close to initial state mutually.This process is not only more loaded down with trivial details, and electrolyte life cycle is short, and then will consume more electric energy and manpower.
Summary of the invention
In order to prevent the change of positive and negative electrode concentration of electrolyte solutions and the volume brought due to the long-term charge and discharge cycles of battery system, improve the efficiency of battery and the utilance of electrolyte solution, also reduce as much as possible simultaneously due to mixed positive and negative electrode electrolyte solution mutually consume extra electric energy and manpower.Applicant is found by a series of research and experiment, and according to the migratory direction of electrolyte solution in different film, principle that migration velocity is different, be specially in cationic membrane cell, after battery discharge terminates, electrolyte solution moves to positive pole from negative pole; In anionic membrane battery, after battery discharge terminates, electrolyte solution moves to negative pole from positive pole.Between this, inventor by the regulation and control of amount adding both positive and negative polarity electrolyte species, effectively can improve the energy efficiency of battery when carrying out long-term charge and discharge cycles and electrolyte utilance.
The method that the present invention adopts positive and negative electrode electrolyte not wait is in a state relatively stably for a long time to make the battery capacity of flow battery.Therefore, an object of the present invention is to provide a kind of vanadium redox battery, comprise the composition anode electrolyte of vanadium redox battery and electrolyte liquid, electrolyte utilance and battery efficiency when the present invention keeps battery long-time running by the regulation and control of the volume to the anode electrolyte added at first and electrolyte liquid.
Concrete, all-vanadium liquid flow energy storage battery comprises anolyte liquid storage tank, cathode electrolyte storage tank, anode electrolyte are stored in anolyte liquid storage tank, electrolyte liquid is stored in cathode electrolyte storage tank, before battery operation starts, tetravalent vanadium ion sulfuric acid solution is added in anolyte liquid storage tank, add trivalent vanadium ion sulfuric acid solution in cathode electrolyte storage tank, and ensure that in both positive and negative polarity electrolyte, total vanadium ion concentration is all equal with sulfate concentration; Or before battery operation starts, in both positive and negative polarity electrolyte storage tank, add the sulfuric acid solution of same three, tetravalent vanadium ion mixed in equal amounts.Positive and negative electrode electrolyte total V density is 0.8 ~ 2.5mol/L, and sulfate concentration is 1 ~ 5mol/L.
When battery diaphragm is cation-exchange membrane, when battery carries out multi cycle operation, electrolyte will move to positive pole fluid reservoir from negative pole fluid reservoir, and the volume ratio of the anode electrolyte at this moment added at first and electrolyte liquid is between 1/1.2 ~ 1/5.
When battery diaphragm is anion-exchange membrane, when battery carries out multi cycle operation, electrolyte will move to negative pole fluid reservoir from positive pole fluid reservoir, and the volume ratio of the anode electrolyte at this moment added at first and electrolyte liquid is between 5/1 ~ 1.2/1.
Beneficial outcomes of the present invention:
(1) the present invention can when battery long-time running, and the effective electrolyte utilance improving battery, reduces battery cost.
(2) the present invention effectively reduces the adverse effect brought to battery by concentration polarization, improves the efficiency of battery to a certain extent.
(3) do not adopt the mutual mixing device of positive and negative electrode electrolyte in the system of flow battery of the present invention, greatly reduce the cost of flow battery.
(4) flow battery system of the present invention is installed simple, safeguards easily.
Embodiment
An object of the present invention is to provide a kind of vanadium redox battery, comprise the composition anode electrolyte of vanadium redox battery and electrolyte liquid, electrolyte utilance and battery efficiency when it is characterized in that the present invention keeps battery long-time running by the regulation and control of the volume to the anode electrolyte added at first and electrolyte liquid.
Concrete, all-vanadium liquid flow energy storage battery comprises anolyte liquid storage tank, cathode electrolyte storage tank, anode electrolyte are stored in anolyte liquid storage tank, electrolyte liquid is stored in cathode electrolyte storage tank, before battery operation starts, tetravalent vanadium ion sulfuric acid solution is added in anolyte liquid storage tank, add trivalent vanadium ion sulfuric acid solution in cathode electrolyte storage tank, and ensure that in both positive and negative polarity electrolyte, total vanadium ion concentration is all equal with sulfate concentration; Or before battery operation starts, in both positive and negative polarity electrolyte storage tank, add the sulfuric acid solution of same three, tetravalent vanadium ion mixed in equal amounts.Positive and negative electrode electrolyte total V density is 0.8 ~ 2.5mol/L, and sulfate concentration is 1 ~ 5mol/L.
When battery diaphragm is cation-exchange membrane, when battery carries out multi cycle operation, electrolyte will move to positive pole fluid reservoir from negative pole fluid reservoir, and the volume ratio of the anode electrolyte at this moment added at first and electrolyte liquid is between 1/1.2 ~ 1/5.
When battery diaphragm is anion-exchange membrane, when battery carries out multi cycle operation, electrolyte will move to negative pole fluid reservoir from positive pole fluid reservoir, and the volume ratio of the anode electrolyte at this moment added at first and electrolyte liquid is between 5/1 ~ 1.2/1.
In a preferred embodiment, before battery operation starts, tetravalent vanadium ion sulfuric acid solution is added in anolyte liquid storage tank, trivalent vanadium ion sulfuric acid solution is added in cathode electrolyte storage tank, in positive and negative electrode electrolyte, total V density is 1.0 ~ 2.3mol/L, sulfate concentration is 1.5 ~ 4.5mol/L, and ensures that in both positive and negative polarity electrolyte, total vanadium ion concentration is all equal with sulfate concentration.When battery diaphragm is cation-exchange membrane, when battery carries out multi cycle operation, electrolyte will move to positive pole fluid reservoir from negative pole fluid reservoir, and the volume ratio of the anode electrolyte at this moment added at first and electrolyte liquid is between 1/1.8 ~ 1/4.When battery diaphragm is anion-exchange membrane, when battery carries out multi cycle operation, electrolyte will move to negative pole fluid reservoir from positive pole fluid reservoir, and the volume ratio of the anode electrolyte at this moment added at first and electrolyte liquid is between 4/1 ~ 1.8/1.
In a more preferred, before battery operation starts, tetravalent vanadium ion sulfuric acid solution is added in anolyte liquid storage tank, trivalent vanadium ion sulfuric acid solution is added in cathode electrolyte storage tank, in positive and negative electrode electrolyte, total V density is 1.2 ~ 2.0mol/L, sulfate concentration is 2 ~ 4mol/L, and ensures that in both positive and negative polarity electrolyte, total vanadium ion concentration is all equal with sulfate concentration.When battery diaphragm is cation-exchange membrane, when battery carries out multi cycle operation, electrolyte will move to positive pole fluid reservoir from negative pole fluid reservoir, and the volume ratio of the anode electrolyte at this moment added at first and electrolyte liquid is between 1/2 ~ 1/3.When battery diaphragm is anion-exchange membrane, when battery carries out multi cycle operation, electrolyte will move to negative pole fluid reservoir from positive pole fluid reservoir, and the volume ratio of the anode electrolyte at this moment added at first and electrolyte liquid is between 3/1 ~ 2/1.
In a most preferred embodiment, before battery operation starts, tetravalent vanadium ion sulfuric acid solution is added in anolyte liquid storage tank, trivalent vanadium ion sulfuric acid solution is added in cathode electrolyte storage tank, in positive and negative electrode electrolyte, total V density is 1.4 ~ 1.8mol/L, sulfate concentration is 2.5 ~ 3.5mol/L, and ensures that in both positive and negative polarity electrolyte, total vanadium ion concentration is all equal with sulfate concentration.When battery diaphragm is cation-exchange membrane, when battery carries out multi cycle operation, electrolyte will move to positive pole fluid reservoir from negative pole fluid reservoir, and the volume ratio of the anode electrolyte at this moment added at first and electrolyte liquid is between 1/2.2 ~ 1/2.7.When battery diaphragm is anion-exchange membrane, when battery carries out multi cycle operation, electrolyte will move to negative pole fluid reservoir from positive pole fluid reservoir, and the volume ratio of the anode electrolyte at this moment added at first and electrolyte liquid is between 2.7/1 ~ 2.2/1.
The present invention is the principle different according to the migratory direction of electrolyte solution in different film, by the regulation and control adding both positive and negative polarity electrolyte volume, effectively can improve the energy efficiency of battery when carrying out long-term charge and discharge cycles and electrolyte utilance.
Embodiment
In further detail the present invention is described for vanadium redox battery below, but the present invention is not limited only to this.
1. this battery system is made up of a joint monocell;
2. battery cation-exchange membrane is as the barrier film of battery;
3. cell reaction area is 100cm
2.
4. electrolyte solution (anode electrolyte and electrolyte liquid) vanadium ion (trivalent and tetravalent vanadium ion concentration are respectively 0.75mol/L) concentration is 1.5mol/L, and sulfate concentration is 3mol/L;
5. positive and negative electrode electrolyte total amount is 200mL;
6. the current density of battery constant current charging-discharging is 80mA/cm
2;
7. single battery discharge and recharge cut-off battery is respectively 1.55V and 1.0V.
Embodiment 1
The volume ratio of the anode electrolyte that tested vanadium redox battery adds at first and electrolyte liquid is 9/11, and namely anode addition is 90mL, and negative pole addition is 110mL.After 200 circulations are carried out in experiment, record related data.
Embodiment 2
The volume ratio of the anode electrolyte that tested vanadium redox battery adds at first and electrolyte liquid is 2/3, and namely anode addition is 80mL, and negative pole addition is 120mL.After 200 circulations are carried out in experiment, record related data.
Embodiment 3
The volume ratio of the anode electrolyte that tested vanadium redox battery adds at first and electrolyte liquid is 7/13, and namely anode addition is 70mL, and negative pole addition is 130mL.After 200 circulations are carried out in experiment, record related data.
Embodiment 4
The volume ratio of the anode electrolyte that tested vanadium redox battery adds at first and electrolyte liquid is 3/7, and namely anode addition is 60mL, and negative pole addition is 140mL.After 200 circulations are carried out in experiment, record related data.
Embodiment 5
The volume ratio of the anode electrolyte that tested vanadium redox battery adds at first and electrolyte liquid is 1/3, and namely anode addition is 50mL, and negative pole addition is 150mL.After 200 circulations are carried out in experiment, record related data.
Embodiment 6
The volume ratio of the anode electrolyte that tested vanadium redox battery adds at first and electrolyte liquid is 1/4, and namely anode addition is 40mL, and negative pole addition is 160mL.After 200 circulations are carried out in experiment, record related data.
Comparative example 1
The volume ratio of the anode electrolyte that tested vanadium redox battery adds at first and electrolyte liquid is 1/1, and namely anode addition is 100mL, and negative pole addition is 100mL.After 200 circulations are carried out in experiment, record related data.
Test:
Arbin BT-2000 battery charging and discharging instrument (manufacture of Arbin company of the U.S.) is adopted to carry out charge-discharge test to battery.Test result is as shown in table 1.
Table 1
As can be seen from the above table, redox flow batteries according to the present invention is after 200 charge and discharge cycles: 1. the average energy efficiency of redox flow batteries has all exceeded 81.5%; 2. electrolyte solution average utilization is also more than 55%.By contrast, the redox flow batteries in comparative example, after 200 charge and discharge cycles, the average energy efficiency of battery only has 81.1, and average electrolyte utilance also only has 50.1%.Pass through the present invention, align, the initial incremental amount of electrolyte liquid carries out the distribution of proper ratio, after battery operation 200 circulation, the average energy efficiency of battery can improve about 2 percentage points, and average electrolyte utilance also has the raising of about 15 percentage points.
Claims (3)
1. a vanadium redox battery control method, comprises battery diaphragm, anolyte liquid storage tank, cathode electrolyte storage tank, and anode electrolyte is stored in anolyte liquid storage tank, and electrolyte liquid is stored in cathode electrolyte storage tank; It is characterized in that:
When battery diaphragm is cation-exchange membrane, before battery operation, the volume ratio of the electrolyte liquid adding the anode electrolyte in anolyte liquid storage tank and add in cathode electrolyte storage tank is between 1/1.2 ~ 1/5;
Or when battery diaphragm is anion-exchange membrane, before battery operation, the volume ratio of the electrolyte liquid adding the anode electrolyte in anolyte liquid storage tank and add in cathode electrolyte storage tank is between 5/1 ~ 1.5/1.
2. control method as claimed in claim 1, is characterized in that:
Anode electrolyte is the sulfuric acid solution of tetravalent vanadium ion, and electrolyte liquid is the sulfuric acid solution of trivalent vanadium ion, and ensures that in anode electrolyte and electrolyte liquid, vanadium ion concentration is all equal with sulfate concentration;
Or by the mixing of the sulfuric acid solution of the sulfuric acid solution of tetravalent vanadium ion and trivalent vanadium ion, in mixed liquor, the concentration of tetravalent vanadium ion and trivalent vanadium ion is equal, mixed liquor not only as anode electrolyte, but also simultaneously as electrolyte liquid.
3. control method as claimed in claim 2, is characterized in that:
Before battery operation starts, in anolyte liquid storage tank, in cathode electrolyte storage tank, add anode electrolyte and electrolyte liquid respectively;
In anode electrolyte, electrolyte liquid, total V density is respectively 0.8 ~ 2.5mol/L, and sulfate concentration is 1 ~ 5mol/L.
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| CN201310454929.7A CN104518228A (en) | 2013-09-29 | 2013-09-29 | All-vanadium oxidation reduction flow battery adjusting method |
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| CN201310454929.7A CN104518228A (en) | 2013-09-29 | 2013-09-29 | All-vanadium oxidation reduction flow battery adjusting method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017156679A1 (en) * | 2016-03-14 | 2017-09-21 | 大连融科储能技术发展有限公司 | Adjustment and control method for flow battery and adjustment and control system thereof, and flow battery |
| CN116231024A (en) * | 2023-04-11 | 2023-06-06 | 西安西域美唐电竞科技有限公司 | Energy storage method of all-vanadium liquid flow energy storage device |
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| CN101619465A (en) * | 2008-07-02 | 2010-01-06 | 中国科学院大连化学物理研究所 | Method for preparing vanadium battery solution or adjusting capacity and special device thereof |
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- 2013-09-29 CN CN201310454929.7A patent/CN104518228A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619465A (en) * | 2008-07-02 | 2010-01-06 | 中国科学院大连化学物理研究所 | Method for preparing vanadium battery solution or adjusting capacity and special device thereof |
Non-Patent Citations (1)
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| 肖钢 林茂财: "《大规模化学储能技术》", 30 June 2011 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017156679A1 (en) * | 2016-03-14 | 2017-09-21 | 大连融科储能技术发展有限公司 | Adjustment and control method for flow battery and adjustment and control system thereof, and flow battery |
| US11171350B2 (en) | 2016-03-14 | 2021-11-09 | Dalian Rongkepower Co., Ltd | Flow battery control method, flow battery control system and flow battery |
| US11626605B2 (en) | 2016-03-14 | 2023-04-11 | Dalian Rongkepower Co., Ltd | Flow battery control method, flow battery control system and flow battery |
| CN116231024A (en) * | 2023-04-11 | 2023-06-06 | 西安西域美唐电竞科技有限公司 | Energy storage method of all-vanadium liquid flow energy storage device |
| CN116231024B (en) * | 2023-04-11 | 2023-11-10 | 西安西域美唐电竞科技有限公司 | Energy storage method of all-vanadium liquid flow energy storage device |
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Application publication date: 20150415 |