CN103427103A - Production method for electrolyte for high-purity all-vanadium flow batteries - Google Patents
Production method for electrolyte for high-purity all-vanadium flow batteries Download PDFInfo
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- CN103427103A CN103427103A CN201310323210XA CN201310323210A CN103427103A CN 103427103 A CN103427103 A CN 103427103A CN 201310323210X A CN201310323210X A CN 201310323210XA CN 201310323210 A CN201310323210 A CN 201310323210A CN 103427103 A CN103427103 A CN 103427103A
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- vanadium
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- electrolyte
- vanadium redox
- flow battery
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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
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Abstract
The invention provides a production method for electrolyte for high-purity all-vanadium flow batteries. Vanadium oxide is taken as a main raw material, and the valency state of vanadium is adjusted with a proper method so as to obtain vanadium battery electrolyte with specific concentration and specific valency state at length. The production method has the advantages that the technological process is simple, the operation is easy and the raw material cost is low. The production method mainly comprises the following steps: 1) diluting acid solution, adding concentrated acid into water, stirring uniformly and cooling appropriately; 2) adding vanadium oxide quantificationally, and stirring to dissolve the material to prepare VO<2+> acid solution; 3) adding V2O3 quantificationally, and stirring to dissolve the material; 4) detecting the vanadium concentration and acid radical concentration of solution, adjusting vanadium valency state and acid radical concentration according to detection results, filtering, returning filter residue to next cycle, leading filtrate into an adjusting groove, and performing adjustment to obtain qualified vanadium battery electrolyte.
Description
Technical field
The present invention relates to electrolyte of vanadium redox battery, be specially the production method of a kind of vanadium valence state between the all-vanadium redox flow battery electrolyte of+3 to+4 valencys.
Technical background
In recent years, all-vanadium flow vanadium cell (VRB), as emerging energy-storage battery, was widely used in the thermal energy storage process of wind-powered electricity generation, solar power generation.Electrolyte of vanadium redox battery, as crucial energy-accumulating medium, is the chief component of vanadium cell.
Therefore, low-cost, produce the industrial applications that electrolyte of vanadium redox battery will contribute to vanadium cell on a large scale.
The disclosed technology of CN101174705 is for being used V
2O
5And V
2O
3Mixed-powder is primary raw material, adds suitable additive, uses the electrolytic cell electrolysis to obtain the electrolyte of 5-6mol/l.
The technology that CN102354762 announces adds the sulfuric acid activation for the use vanadic oxide, then adds high-purity reducing agent to be reduced, and by the electrolyte reduction in diaphragm cell of the vanadic sulfate solution of gained, obtains highly purified electrolyte of vanadium redox battery.
The technology that CN101651221 announces, for using in vanadic oxide or vanadium trioxide vitriolization solution, adds the reducing agents such as ascorbic acid, ascorbinase, can directly obtain electrolyte of vanadium redox battery.
The technology that CN101728560 announces is for being used high-purity V
2O
3For raw material, add suitable additive and reducing agent, under the high pure nitrogen protection, directly adopt chemical method to make vanadium redox battery negative pole electrolyte.
The technology that CN102468509 announces is raw material for using ammonium metavanadate and carbonic hydroammonium, and high-temperature calcination obtains V
2O
3, with high-temperature sulfuric acid, dissolve V
2O
3, then add V
2O
5Adjust the vanadium valence state, finally make electrolyte of vanadium redox battery.
The various production methods of above-mentioned electrolyte of vanadium redox battery, have in two steps, at first makes vanadic sulfate, then electrolysis makes the electrolyte of suitable valence state.What have adds the additive roasting, and high-temperature digestion, make electrolyte.
Because the manufacturing cost of electrolytic cell is higher, the regular maintenance difficulty, power is subject to power limitations, so the way of electrolysis is very limited when electrolyte of vanadium redox battery industry large-scale application.
Need to provide a kind of needn't electrolysis, low cost, the electrolyte of vanadium redox battery production technology can be mass-produced.Summary of the invention
The technical problem that the present invention solves is to provide a kind of electrolysis, low cost of not needing, the electrolyte of vanadium redox battery production technology can be mass-produced.
Technical scheme of the present invention is:
With V
2O
5, V
6O
13, V
2O
4, VO
2, V
2O
3In one or more be raw material, with sulfuric acid or dissolving with hydrochloric acid, at first make sulfur acid vanadyl or dichloro vanadyl solution, then add V
2O
3Further make electrolyte of vanadium redox battery.Production method is as follows:
1. the concentrated sulfuric acid or concentrated hydrochloric acid are added to the water, are diluted to finite concentration;
2. by V
2O
5, V
6O
13, V
2O
4, VO
2, V
2O
3In one or more slowly join in the acid of having diluted,
Be stirred to dissolve complete;
3. detect vanadium concentration, vanadium valence state, the acid group concentration of solution;
4. according to testing result, calculate and add V
2O
3, be stirred to dissolve complete, filter;
5. be diluted with water to certain concentration.
In course of reaction, suitably cooling solution, maintain solution temperature.
Advantage of the present invention:
It is raw material that the oxide of vanadium is take in the present invention, does not use any other additive, does not use the electrolytic cell electroreduction, the disposable electrolyte of vanadium redox battery that makes.With respect to electrolysis, this explained hereafter cost greatly reduces, and the maintenance of production equipment is simple, and production operation is simple.
Embodiment
Below will, for the production method of mentioning in summary of the invention, with instantiation, describe, but the present invention be not limited to following examples.
Embodiment 1
Add 3m in container
3Water, the ON cycle cooling water, stir and add 1.9m
392.5% the concentrated sulfuric acid, add 520KgV
2O
4, be stirred to dissolve complete, obtain the pure blue transparency liquid.Detect VO
2+Concentration is 1mol/l, the sulfuric acid of sulfate concentration 5.3mol/l, vanadic sulfate mixed solution.92 ℃ of solution temperatures, add 470KgV
2O
3, be stirred to powder dissolution complete, obtain glaucous transparency liquid, detecting solution vanadium valence state is+3.5.Be diluted with water to vanadium concentration 1.6mol/l, sulfate radical 4.24mol/l.
Embodiment 2
Add 3m in container
3Water, the ON cycle cooling water, stir and add 1.9m
392.5% concentrated sulfuric acid, add 288KgV
2O
5, 93 ℃ of temperature, stir and also slowly add 720KgV
2O
3, to the vanadium valence state be+3.5.Detect vanadium concentration 2.3mol/l, sulfate radical 6.1mol/l, be diluted with water to vanadium concentration 1.6mol/l, sulfate radical 4.24mol/l.
Embodiment 3
Add 3m in container
3Water, the ON cycle cooling water, stir and add 1.9m
392.5% concentrated sulfuric acid, add 410Kg V
6O
13, after stirring 1h, 90 ℃ of temperature, slowly add 600Kg V
2O
3, be stirred to dissolve complete.The vanadium average valence that detects solution is+3.48.Be diluted with water to vanadium concentration 1.61mol/l, sulfate radical
4.16mol/l。
Embodiment 4
Add 0.7m in container
3Water, the ON cycle cooling water, stir and add 2m
3Concentrated hydrochloric acid, add 300KgV
2O
4, be stirred to and dissolve clarification, obtain the pure blue transparency liquid.Detect VO
2+For 2.3mol/l, be heated to 90 ℃ and add 275KgV
2O
3, continue to be stirred to the dissolution of solid clarification.Detecting the vanadium average valence is+3.51.Dilute vanadium concentration to 2.5mol/l, chloride ion 6.7mol/l.
Embodiment 5
Add 0.85m in container
3Water, the ON cycle cooling water, stir and add 2.3m
3Concentrated hydrochloric acid, add 165KgV
2O
5, be heated to 90 ℃, stir and also slowly add 400KgV
2O
3, to the vanadium valence state be+3.5.Detect vanadium concentration 2.3mol/l, chloride ion 6.1mol/l, be diluted with water to vanadium concentration 2.5mol/l, chloride ion 8mol/l.
Embodiment 6
Add 1m in container
3Water, the ON cycle cooling water, stir and add 4.1m
3Concentrated hydrochloric acid, add 410KgV
6O
13, after stirring 1h, be heated to 90 ℃, slowly add 600Kg V
2O
3, be stirred to dissolve complete.The vanadium average valence that detects solution is+3.52.Be diluted with water to vanadium concentration 2.51mol/l, chloride ion 8.05mol/l.
Claims (10)
1. the production method of an all-vanadium redox flow battery electrolyte, is characterized in that: take barium oxide as primary raw material, with strong acid, dissolve barium oxide, at first make VO
2+Solution, utilize exothermic heat of reaction, the solution holding temperature, at 80 ℃-100 ℃, adds V
2O
3Stirring and dissolving, finally obtain the V electrolyte that the vanadium valence state is qualified.
2. according to the production method of all-vanadium redox flow battery electrolyte claimed in claim 1, it is characterized in that: add V
2O
3Before, the temperature of solution preferably should be between 90 ℃-95 ℃.
3. according to the production method of all-vanadium redox flow battery electrolyte claimed in claim 1, it is characterized in that: described barium oxide comprises V
2O
5, V
6O
13, V
2O
4, VO
2, V
2O
3In one or two or more kinds.
4. according to the production method of all-vanadium redox flow battery electrolyte claimed in claim 1, it is characterized in that: the strong acid used is the mass concentration 92.5-98% concentrated sulfuric acid or mass concentration 31-38% hydrochloric acid.
5. according to the production method of all-vanadium redox flow battery electrolyte claimed in claim 1, it is characterized in that: resulting product is H
2SO
4VOSO
4V
2(SO
4)
3Solution mixture or HCl VOCl
2VCl
3Solution mixture.
6. according to the production method of all-vanadium redox flow battery electrolyte claimed in claim 1, it is characterized in that: the vanadium concentration of gained electrolyte of vanadium redox battery is 1-3mol/l.
7. according to the production method of all-vanadium redox flow battery electrolyte claimed in claim 1, it is characterized in that: the vanadium valence state is qualified refers to that the vanadium valence state is controlled between+3 to+4.
8. according to the production method of all-vanadium redox flow battery electrolyte claimed in claim 1, it is characterized in that: the V adopted
2O
3Content of vanadium is 67-68%.
9. according to the production method of all-vanadium redox flow battery electrolyte claimed in claim 1, it is characterized in that:
The employing barium oxide is primary raw material, by acid adding, dissolves, and further electrolysis, can directly make V electrolyte;
At first the oxide with vanadium makes pure VO
2+Solution, then add V
2O
3, further make electrolyte of vanadium redox battery.
10. according to the production method of all-vanadium redox flow battery electrolyte claimed in claim 1, it is characterized in that:
Detailed process is as follows:
1) dilute acid solutions, be added to the water the concentrated sulfuric acid or concentrated hydrochloric acid, and stir, holding temperature >=60 ℃;
2) add barium oxide, be stirred to material dissolution, make VO
2+Acid solution;
3) keep solution temperature>=90 ℃ to add V
2O
3, be stirred to material dissolution.
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|---|---|---|---|
| CN201310323210XA CN103427103A (en) | 2013-07-29 | 2013-07-29 | Production method for electrolyte for high-purity all-vanadium flow batteries |
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|---|---|---|---|
| CN201310323210XA CN103427103A (en) | 2013-07-29 | 2013-07-29 | Production method for electrolyte for high-purity all-vanadium flow batteries |
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| CN103427103A true CN103427103A (en) | 2013-12-04 |
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ID=49651544
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103904343A (en) * | 2014-04-02 | 2014-07-02 | 四川大学 | Preparation method of electrolyte for all-vanadium redox flow battery |
| CN106129441A (en) * | 2016-06-29 | 2016-11-16 | 河北钢铁股份有限公司承德分公司 | The cleaning fast preparation method of a kind of vanadium oxysulfate solution and purposes |
| WO2017128967A1 (en) * | 2016-01-28 | 2017-08-03 | 中国科学院过程工程研究所 | System and method for producing high-purity high-activity vanadium electrolyte |
| CN107069066A (en) * | 2017-03-13 | 2017-08-18 | 河南弘康光能科技有限公司 | A kind of all-vanadium redox flow battery electrolyte and its compound method |
| CN109065906A (en) * | 2018-09-27 | 2018-12-21 | 成都先进金属材料产业技术研究院有限公司 | The regeneration method of failure electrolyte of vanadium redox battery |
| CN109148910A (en) * | 2018-09-27 | 2019-01-04 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for the electrolyte liquid regeneration V electrolyte of failure vanadium cell |
| CN109148911A (en) * | 2018-09-27 | 2019-01-04 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for the anode electrolyte regeneration V electrolyte of failure vanadium cell |
| CN107565153B (en) * | 2016-07-01 | 2019-12-13 | 中国科学院过程工程研究所 | system and method for preparing high-activity high-purity specific valence vanadium electrolyte |
| WO2020035037A1 (en) * | 2018-08-16 | 2020-02-20 | 江苏泛宇能源有限公司 | Method for preparing liquid flow battery electrolyte |
| WO2020038411A1 (en) * | 2018-08-24 | 2020-02-27 | 江苏泛宇能源有限公司 | Waste gas treatment method for flow battery and flow battery system |
| TWI754595B (en) * | 2021-06-03 | 2022-02-01 | 虹京金屬股份有限公司 | Method for manufacturing vanadium electrolyte |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103904343B (en) * | 2014-04-02 | 2017-03-15 | 四川大学 | The preparation method of all-vanadium redox flow battery electrolytic solution |
| CN103904343A (en) * | 2014-04-02 | 2014-07-02 | 四川大学 | Preparation method of electrolyte for all-vanadium redox flow battery |
| WO2017128967A1 (en) * | 2016-01-28 | 2017-08-03 | 中国科学院过程工程研究所 | System and method for producing high-purity high-activity vanadium electrolyte |
| CN106129441A (en) * | 2016-06-29 | 2016-11-16 | 河北钢铁股份有限公司承德分公司 | The cleaning fast preparation method of a kind of vanadium oxysulfate solution and purposes |
| CN107565153B (en) * | 2016-07-01 | 2019-12-13 | 中国科学院过程工程研究所 | system and method for preparing high-activity high-purity specific valence vanadium electrolyte |
| CN107069066A (en) * | 2017-03-13 | 2017-08-18 | 河南弘康光能科技有限公司 | A kind of all-vanadium redox flow battery electrolyte and its compound method |
| CN107069066B (en) * | 2017-03-13 | 2020-09-08 | 河南弘康光能科技有限公司 | All-vanadium redox flow battery electrolyte and preparation method thereof |
| WO2020035037A1 (en) * | 2018-08-16 | 2020-02-20 | 江苏泛宇能源有限公司 | Method for preparing liquid flow battery electrolyte |
| WO2020038411A1 (en) * | 2018-08-24 | 2020-02-27 | 江苏泛宇能源有限公司 | Waste gas treatment method for flow battery and flow battery system |
| CN109148911A (en) * | 2018-09-27 | 2019-01-04 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for the anode electrolyte regeneration V electrolyte of failure vanadium cell |
| CN109148910A (en) * | 2018-09-27 | 2019-01-04 | 成都先进金属材料产业技术研究院有限公司 | Utilize the method for the electrolyte liquid regeneration V electrolyte of failure vanadium cell |
| CN109065906A (en) * | 2018-09-27 | 2018-12-21 | 成都先进金属材料产业技术研究院有限公司 | The regeneration method of failure electrolyte of vanadium redox battery |
| TWI754595B (en) * | 2021-06-03 | 2022-02-01 | 虹京金屬股份有限公司 | Method for manufacturing vanadium electrolyte |
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Application publication date: 20131204 |