CN109841875A - A kind of all-vanadium flow battery energy-storage module electrolyte valence state balance control method - Google Patents
A kind of all-vanadium flow battery energy-storage module electrolyte valence state balance control method Download PDFInfo
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- CN109841875A CN109841875A CN201910216996.2A CN201910216996A CN109841875A CN 109841875 A CN109841875 A CN 109841875A CN 201910216996 A CN201910216996 A CN 201910216996A CN 109841875 A CN109841875 A CN 109841875A
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Abstract
The present invention provides a kind of all-vanadium flow battery energy-storage module electrolyte valence state balance control method, pass through an electrolyte valence state reduction apparatus in parallel in electrolyte liquid pipe road, the valence state of electrolyte in all-vanadium flow battery energy-storage module is reduced by the method for electrolysis, when valence state reaches balance, stop electrolysis.The present invention passes through an electrolyte valence state reduction apparatus in parallel in electrolyte liquid pipe road, it only needs to consume electric energy, it does not need to increase other materials in energy-storage module, makes full use of the pump and pipeline of energy-storage module, it is not only easy to use, it is easy to operate, and cost of labor can be effectively reduced in relatively other methods, meanwhile, on-line operation can be carried out, under conditions of not stopping energy-storage module operation, achieve the purpose that the reduction of energy-storage module electrolyte whole valence state.
Description
Technical field
The present invention relates to flow battery technology fields, and in particular to a kind of electrolyte of vanadium redox battery valence state balance method.
Background technique
All-vanadium flow battery has power capacity as a kind of energy-storage battery designed exclusively for scale power energy storage
Independent design is easy to the advantages that extension, operational safety, long service life and electrolyte are Ke Xunhuanliyong, is on a large scale and to divide
One of key links in fields such as the access of cloth new energy, smart grid.All-vanadium liquid flow energy storage battery is that will have different valence state
Vanadium ion solution respectively as anode and cathode active material, be separately stored in respective electrolyte storage tank.Electrolyte
By the effect of pump, the cathode chamber and anode chamber of battery are flowed separately through by external receiver circulation, and oxygen occurs in electrode surface
Change and reduction reaction realize the charge and discharge to battery.
All-vanadium flow battery energy-storage system will appear in the long-term use positive and negative anodes two sides vanadium ion infiltration and
Various side reactions cause electrolyte whole valence state to increase, and pile charge/discharge capacity reduces, and can continue to reduce energy storage without maintenance
The capacity of system seriously affects the performance of energy-storage system.In the prior art, usually by anode electrolyte be added valence state compared with
Low electrolyte reduces valence state, or will refill again after the extraction reduction of high-valence state electrolyte.
Chinese patent literature CN201410040024.X discloses the method for vanadium cell and its electrolyte rebalancing, the patent
It is passed through Low Valent Vanadium solion to anolyte liquid storage tank by Low Valent Vanadium solion feeding mechanism, neutralizes pentavalent vanadium therein
Ion.High price vanadium ion extra in high price vanadium ion solution recovery device recycling anolyte liquid storage tank can also be used molten
Liquid, to reduce the difference of the mole of vanadium ion in positive and negative anodes electrolyte.In Low Valent Vanadium solion and positive vanadium ion solution
In Blending Processes, it is also necessary to sulfuric acid is added and water adjusts the concentration and volume of sulfuric acid in electrolyte, it is complicated for operation.This method can only
Electrolyte is adjusted outside vanadium energy storage system, maintenance speed is slow, at high cost.
Chinese patent CN200810012119.5 disclose a kind of preparation of vanadium battery solution or the method for capacity regulating and
Dedicated unit, on-line control mode are that electrolysis unit is connected on to the outlet and positive solution of all-vanadium flow battery positive solution
Between storage tank, the anolyte for being stored in anode electrolysis liquid storage tank is made to pass through electric tank cathode by way of forced convertion,
Electrolyte is restored by electrolysis mode, generates oxygen in the anode of electrolytic cell, this method induced positive electrode electrolyte does not restore
Electrolyte liquid.Meanwhile electrolysis unit is connected between anode electrolyte outlet and positive fluid reservoir, pipe-line system resistance compared with
Greatly, being connected in pipeline will lead to energy-storage system and is unable to run.
Therefore, it is necessary to be improved to the prior art.
Summary of the invention
The object of the present invention is to provide a kind of all-vanadium flow battery energy-storage module electrolyte valence state balance control methods, lead to
Cross an electrolyte valence state reduction apparatus in parallel in electrolyte liquid pipe road, it is only necessary to consume electric energy, not need in energy storage mould
Increase other materials in block, makes full use of the pump and pipeline of energy-storage module, not only easy to use, easy to operate, Er Qiexiang
Cost of labor can be effectively reduced to other methods.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of all-vanadium flow battery energy-storage module electrolyte valence state balance control method, by electrolyte liquid pipe road
Middle electrolyte valence state reduction apparatus in parallel reduces electrolyte in all-vanadium flow battery energy-storage module by the method for electrolysis
Valence state stops electrolysis when valence state reaches balance.
According to above scheme, the electrolyte valence state reduction apparatus includes cathode liquid outlet, cathode inlet, electrolysis dress
It sets, positive liquid pump, reduction apparatus anode fluid reservoir, the electrode of the electrolysis unit is oxidation resistant material, the cathode liquid outlet,
Cathode inlet is connected to by pipeline and valve with the cathode fluid reservoir in the energy-storage module.
According to above scheme, equipped with the electrolyte for improving pure water electric conductivity in the reduction apparatus anode fluid reservoir
Aqueous solution, the electrolyte are the sulfuric acid solution that concentration is 1-7mol/L.
According to above scheme, the cathode liquid outlet of the electrolyte valence state reduction apparatus, cathode inlet by pipeline and
Valve is connected to the negative electrode solution main pipeline in the energy-storage module, in parallel with the negative electrode solution pipeline of pile in energy-storage module of entering,
To reduce the resistance in electrolyte electrolytic process.
According to above scheme, the anode of the electrolyte valence state reduction apparatus is equipped with exhaust apparatus, and the exhaust setting exists
On the reduction apparatus anode fluid reservoir.
According to above scheme, the cathode of the electrolyte valence state reduction apparatus is passed through nitrogen, directly to the energy-storage module
Cathode supplements nitrogen.
Basic functional principle of the invention:
Isolated operation mode: it after electrolyte valence state reduction apparatus is connected to the negative electrode solution pipeline of energy-storage module, closes and corresponds to
Energy-storage module negative electrode solution enter pile valve when, make electrolyte liquid pass through electrolyte valence state reduction apparatus run, will high price
The negative electrode solution of state is reduced into lower valency, when valence state reaches balance, stops electrolysis, restores energy-storage module work.
On-line operation mode: it after electrolyte valence state reduction apparatus is connected to the negative electrode solution pipeline of energy-storage module, does not close pair
Answer energy-storage module negative electrode solution to enter the valve of pile, so that electrolyte liquid a part is entered pile, a part enter it is of the invention
Electrolyte valence state reduction apparatus in the case where not influencing energy-storage module work, while carrying out the reduction of negative electrode solution, online to transport
Row, is reduced into lower valency for the negative electrode solution of high-valence state, when valence state reaches balance, stops electrolysis.Meanwhile it can be electrolysed by control
The flow and electric current of the cathode inlet switch size of liquid valence state reduction apparatus, pump, the speed that control electrolyte is reduced.
The beneficial effects of the present invention are:
1) present invention reduces the valence state of electrolyte by way of electrolysis, not add in energy-storage module electrolyte other
Substance carries out other operations, simple and easy to do；
2) present invention makes full use of the pipeline, pump, power supply of all-vanadium flow battery energy-storage module, and device structure is simple, installation
It is easy with removing, electrolysis procedure is simple, and electrolyte reduction process carries out while can running with energy-storage module, will not influence energy storage
Module work is also convenient for supplement nitrogen；
3) electrolyte reduction process of the invention only needs water consumption, no discharge, clean and environmental protection, and relatively other methods can be effective
Reduce cost of labor.
4) present invention can carry out on-line operation, under conditions of not stopping energy-storage module operation, reach energy-storage module electricity
Solve the purpose that liquid entirety valence state reduces.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of electrolyte valence state reduction apparatus of the invention；
Fig. 2 is electrolyte valence state reduction apparatus access energy-storage module optimum position schematic diagram of the invention.
In figure: 1, cathode liquid outlet；2, cathode inlet；3, electrolysis unit；4, positive liquid pump；5, reduction apparatus anode stores up
Flow container；6, energy-storage module cathode fluid reservoir；7, electrolyte valence state reduction apparatus；8, pile；9, energy-storage module anode fluid reservoir；
10, negative pump；11, positive pump.
Specific embodiment
Technical solution of the present invention is illustrated with embodiment with reference to the accompanying drawing.
Embodiment 1 is shown in Fig. 1 to Fig. 2:
The present invention provides a kind of all-vanadium flow battery energy-storage module electrolyte valence state balance control method: for 100kW
All-vanadium flow battery energy-storage module, electrolyte whole valence state is higher, and anode electrolyte valence state is higher, and electrolyte liquid valence state is just
Often, its anode of electrolyte valence state reduction apparatus uses the dilution heat of sulfuric acid of 2mol/L, and cathode is connected to 100kW all-vanadium flow battery
In energy-storage module electrolyte liquid main line, and 100kW all-vanadium flow battery energy-storage module pile is bypassed, and close parallel connection part
Pipe valve；In energy-storage module situation out of service, start the pump of 100kW all-vanadium flow battery energy-storage module pile cathode,
Start the pump of electrolyte reduction apparatus cathode, opens electrolysis unit power supply, be electrolysed；When 100kW all-vanadium flow battery energy storage
Module negative electrolyte valence state when positive and negative anodes entirety valence state drops to 3.5 valence, stops electrolysis, removes electrolyte valence state reduction apparatus,
Restore energy-storage module pipeline.
Further, the electrolyte valence state reduction apparatus 7 includes cathode liquid outlet 1, cathode inlet 2, electrolysis unit
3, the electrode of positive liquid pump 4, reduction apparatus anode fluid reservoir 5, the electrolysis unit 3 is oxidation resistant material, and the cathode goes out liquid
Mouth 1, cathode inlet 2 are connected to the cathode fluid reservoir 6 in the energy-storage module (see Fig. 1 and Fig. 2) by pipeline and valve.
Electrolyte valence state reduction apparatus 7 of the invention accesses energy-storage module optimum position schematic diagram as shown in Fig. 2, the storage
Energy module includes energy-storage module cathode fluid reservoir 6, pile 8, energy-storage module anode fluid reservoir 9, negative pump 10, positive pump 11.
Embodiment 2:
The present invention provides a kind of all-vanadium flow battery energy-storage module electrolyte valence state balance control method: for 300kW
All-vanadium flow battery energy-storage module, electrolyte whole valence state is higher, and positive valence state is about 4.5 valences, and cathode valence state is about 2.8
Valence, its anode of electrolyte valence state reduction apparatus use the dilution heat of sulfuric acid of 4mol/L, and cathode is connected to 300kW all-vanadium flow battery
In energy-storage module electrolyte liquid main line, and bypass 300kW all-vanadium flow battery energy-storage module pile；Start the full vanadium of 300kW
Flow battery energy storage module is opened electrolysis unit power supply, is electrolysed under conditions of energy-storage module operation；When the full vanadium of 300kW
When flow battery energy storage module anode electrolyte and electrolyte liquid totality valence state reach 3.5 valence, stop electrolysis, removes electrolyte
Valence state reduction apparatus restores energy-storage module pipeline.
The above embodiments are only used to illustrate and not limit the technical solutions of the present invention, although above-described embodiment to the present invention into
Gone detailed description, the related technical personnel of this field it is understood that can modify to the present invention or replace on an equal basis, but
Any modification and part replacement for not departing from spirit and scope of the invention should all be covered in scope of the presently claimed invention.
Claims (6)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114094148A (en) * | 2022-01-19 | 2022-02-25 | 杭州德海艾科能源科技有限公司 | Online capacity recovery method for all-vanadium redox flow battery |
| CN115692808A (en) * | 2022-10-28 | 2023-02-03 | 上海电气(安徽)储能科技有限公司 | All-vanadium redox flow battery electrolyte reduction system and capacity recovery method |
| WO2024251016A1 (en) * | 2023-06-06 | 2024-12-12 | 北京普能世纪科技有限公司 | Capacity recovery method for vanadium redox flow battery |
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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 |
| CN201981262U (en) * | 2010-12-06 | 2011-09-21 | 上海林洋储能科技有限公司 | Circular electrolysis reacting device for preparing electrolyte of vanadium batter |
| US20150056525A1 (en) * | 2013-08-26 | 2015-02-26 | New Well Co., Ltd. | Method for preparing electrolyte for vanadium redox flow battery using vanadium oxide |
| CN204257760U (en) * | 2014-10-21 | 2015-04-08 | 国网电力科学研究院武汉南瑞有限责任公司 | The online recovery device of a kind of mobile high-power type all-vanadium redox flow battery electrolyte |
| CN204651405U (en) * | 2015-04-09 | 2015-09-16 | 深圳市万越新能源科技有限公司 | A kind of experimental provision carrying out the research of vanadium redox battery heap |
| CN204668400U (en) * | 2015-06-12 | 2015-09-23 | 国网电力科学研究院武汉南瑞有限责任公司 | A kind of electrolysis unit of all-vanadium redox flow battery electrolyte |
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- 2019-03-21 CN CN201910216996.2A patent/CN109841875A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN201981262U (en) * | 2010-12-06 | 2011-09-21 | 上海林洋储能科技有限公司 | Circular electrolysis reacting device for preparing electrolyte of vanadium batter |
| US20150056525A1 (en) * | 2013-08-26 | 2015-02-26 | New Well Co., Ltd. | Method for preparing electrolyte for vanadium redox flow battery using vanadium oxide |
| CN204257760U (en) * | 2014-10-21 | 2015-04-08 | 国网电力科学研究院武汉南瑞有限责任公司 | The online recovery device of a kind of mobile high-power type all-vanadium redox flow battery electrolyte |
| CN204651405U (en) * | 2015-04-09 | 2015-09-16 | 深圳市万越新能源科技有限公司 | A kind of experimental provision carrying out the research of vanadium redox battery heap |
| CN204668400U (en) * | 2015-06-12 | 2015-09-23 | 国网电力科学研究院武汉南瑞有限责任公司 | A kind of electrolysis unit of all-vanadium redox flow battery electrolyte |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114094148A (en) * | 2022-01-19 | 2022-02-25 | 杭州德海艾科能源科技有限公司 | Online capacity recovery method for all-vanadium redox flow battery |
| CN115692808A (en) * | 2022-10-28 | 2023-02-03 | 上海电气(安徽)储能科技有限公司 | All-vanadium redox flow battery electrolyte reduction system and capacity recovery method |
| WO2024251016A1 (en) * | 2023-06-06 | 2024-12-12 | 北京普能世纪科技有限公司 | Capacity recovery method for vanadium redox flow battery |
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