CN103606694B - Preparation method for commercial vanadium battery electrolyte - Google Patents
Preparation method for commercial vanadium battery electrolyte Download PDFInfo
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- CN103606694B CN103606694B CN201310568546.2A CN201310568546A CN103606694B CN 103606694 B CN103606694 B CN 103606694B CN 201310568546 A CN201310568546 A CN 201310568546A CN 103606694 B CN103606694 B CN 103606694B
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
- H01M2300/0011—Sulfuric acid-based
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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 discloses a preparation method for commercial vanadium battery electrolyte. According to the preparation method, vanadium electrolyte is prepared by one step through a chemical method; the preparation method comprises the following steps: dissolving raw materials containing vanadium by using an alkali; adjusting a pH (Potential of Hydrogen) value by acid-alkali regulation; repeatedly precipitating the vanadium to remove impurity elements; then roasting to obtain an oxide of the vanadium; finally, dissolving the oxide of the vanadium by using concentrated sulfuric acid to obtain the vanadium electrolyte. With the adoption of the method, impurities including iron, chrome, silicon, manganese and the like can be removed effectively and a process flow is shortened; the vanadium yield is improved, the impurity content is reduced and the process flow is shortened; the product purity can also be improved. The preparation method for the commercial vanadium battery electrolyte has important meanings on production technology levels and market competitiveness of the vanadium electrolyte; the method has good economic benefits and social benefits.
Description
Technical field
The present invention relates to battery manufacturing field, especially a kind of preparation method of electrolyte of vanadium redox battery.
Background technology
In existing liquid energy-storage technology, vanadium redox battery (abbreviation vanadium cell) receives much attention because having stored energy capacitance and power adjustable, big current and can't harm the advantages such as deep discharge, long service life, Operation and Maintenance are simple, environmental protection.Along with the development of correlation technique, vanadium cell just progressively moves towards practical.Vanadium cell forms primarily of three parts: electrode material, battery diaphragm, electrolyte, and therefore its development is also mainly by the restriction of these three aspects.Wherein electrolyte is the core of vanadium cell, and the quality of electrolyte directly determines the energy storage capacity of vanadium cell, finds the suitable method preparing electrolyte of vanadium redox battery to develop important in inhibiting to vanadium cell.
Although the technology of preparing of existing V electrolyte is varied, large mainly with V
2o
5or V
2o
3for raw material, chemical method or electrochemical electrolysis method or both combinations is adopted to prepare V electrolyte.But chemical method prepare the dissolution velocity of solid in the process of electrolyte slow and in reduction process general needs add the reducing agent of picture oxalic acid, sulphur and so on, this kind of material is not easily eradicated, have a small amount of remaining in the electrolytic solution, affect the chemical property of V electrolyte and the useful life of battery.And although electrochemical process technique is simple, in electrolytic process, add additive impurity ion content in electrolyte is increased, cause the charge-discharge performance of electrolyte to reduce, meanwhile anode electrode is easily corroded, and increases preparation cost.
A kind of electrolytic preparation method of all-vanadium redox flow battery electrolyte is provided in patent 03159533.2, this method adopt in the sulfuric acid solution of 1:1, add vanadium trioxide successively, vanadic oxide obtains vanadic sulfate solution, then add the additive such as sodium sulphate, polyoxyethylene nonylphenol ether and carry out electrolysis and obtain the electrolyte of vanadium redox battery that trivalent vanadium and tetravalence vanadium respectively account for total vanadium 50%.
Patent 200710188392.9 provides a kind of preparation method of whole vanadium oxide reduction battery electrolytic solution, this method is after calcining at 100-300 DEG C in electric tube furnace after vanadium trioxide and the concentrated sulfuric acid being mixed by a certain percentage, be dissolved in dilute sulfuric acid, obtain the electrolyte of vanadium redox battery that trivalent vanadium and tetravalence vanadium respectively account for total vanadium 50%.
Patent 200510075608.1 provides a kind of full vanadium ion fluid cell electrolyte and preparation method, this method with the qualified vanadium liquid of vanadium factory for raw material, regulating after pH value with sulfuric acid with liquid sulfur dioxide is that reducing agent reduces, then pH value is regulated to obtain vanadium dioxide precipitation with sodium carbonate, to precipitate in water-soluble, sulfuric acid, ethanolic solution, add additive, then electrolysis obtains the electrolyte of vanadium redox battery that trivalent vanadium and tetravalence vanadium respectively account for total vanadium 50%.
Some problems that the preparation method of above-mentioned V electrolyte also exists, are mainly manifested in:
(1) course of reaction adds additive: additive has an impact to the conductivity of solution and chemical property, and what can cause vanadium oxygen hydrated ion in solution goes hydration, is unfavorable for the dissolving of vanadium.
(2) reaction process is loaded down with trivial details: in course of reaction, and the electrolyte of vanadium redox battery respectively accounting for total vanadium 50% for obtaining trivalent vanadium and tetravalence vanadium needs electrolysis, which increases reaction process, improves preparation cost.
(3) impurity content is high: the impurity content such as V electrolyte institute iron content, chromium, silicon prepared by the experimental raw used according to above-mentioned patent is higher, and these impurity are to the important in useful life of battery.
Therefore, how preparing to utilize and prepare qualified commercial V electrolyte compared with abbreviated system condition, is the difficult problem that existing commercial V electrolyte preparation method faces.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of electrolyte of vanadium redox battery, is that one prepares that impurity content is low, the simple method for preparing vanadium cell electrolyte of technique.
For solving the problems of the technologies described above, the technical solution used in the present invention is: will containing vanadium raw materials alkali heavy molten after, adjust ph is precipitation repeatedly, to remove impurity element wherein, then the oxide of vanadium is obtained by roasting, finally by the oxide dissolution of the concentrated sulfuric acid by vanadium, commercial V electrolyte can be obtained.
Present invention process step is:
(1) will dissolve containing vanadium raw materials alkali lye, adjust ph 7.5 ~ 10, and add cleaner and carry out removal of impurities;
(2) the filtrate adjust ph 1.5 ~ 3.0 after removal of impurities, heating precipitation, obtains ammonium poly-vanadate/ammonium metavanadate;
(3), after being dissolved with alkali by ammonium poly-vanadate/ammonium metavanadate, adjust ph 1.5 ~ 3.0, again precipitation, obtain two heavy ammonium poly-vanadate/ammonium metavanadates;
(4) two heavy ammonium poly-vanadate/ammonium metavanadate roastings under reducibility gas, obtain the oxide of vanadium;
(5) oxide of vanadium mixes with the concentrated sulfuric acid, stirring and dissolving, can obtain V electrolyte.
After adopting this technology, the vanadium product of qualified applicable V electrolyte production generally can be obtained through twice precipitation, if defective, can be passed through more precipitation to reduce the special impurity of vanadium product, obtain the vanadium product that applicable V electrolyte is produced, namely the precipitation process of precipitation process repeatedly can be greater than secondary.
Alkali in step of the present invention (1) is the mixture of NaOH, potassium hydroxide, NaOH and potassium hydroxide, ammoniacal liquor, ammonia or liquefied ammonia.
Cleaner in step of the present invention (1) is aluminium salt cleaner, and described aluminium salt comprises all aluminum soluble salts such as aluminum sulfate, aluminium chloride, sodium metaaluminate.
Reducibility gas in step of the present invention (4) is hydrogen or ammonia; Described sintering temperature is 500 ~ 800 DEG C.
Of the present invention is the vanadium products such as ammonium metavanadate, ammonium poly-vanadate, vanadic oxide, vanadium trioxide and composition thereof containing vanadium raw materials.
The beneficial effect adopting technique scheme to produce is:
(1) purity of V electrolyte is improved: because existing V electrolyte impurity used for all-vanadium redox flow battery is as higher in iron, silicon equal size, strongly limit the useful life of battery; And adopt the present invention to fire highly purified barium oxide after purifying containing vanadium raw materials, can effectively remove the impurity such as iron, chromium, silicon, manganese.
(2) production cost is reduced: the present invention adopts chemical method one step to prepare V electrolyte, shortens technological process, can effectively reduce costs.
Therefore, after adopting the present invention, not only can improve vanadium yield, reduce impurity content, shortened process, thus reduce the production cost of V electrolyte, improve product purity.Have great importance to the production technology level and the market competitiveness that improve V electrolyte, the present invention has good economic benefit and social benefit.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Fig. 1 is schematic flow sheet of the present invention.
Embodiment
Shown in embodiment 1: Fig. 1, the concrete technology of the preparation method of this electrolyte of vanadium redox battery is as described below.
Be raw material with ammonium poly-vanadate, add NaOH and dissolved, by filtrate adjust ph 9, add aluminum sulfate and carry out removal of impurities.By filtrate adjust ph 1.5 after removal of impurities, add heat sink ammonium poly-vanadate.Then by heavy for ammonium poly-vanadate ammoniacal liquor molten after, adjust ph 2.0 sinks ammonium poly-vanadate, filter, dry after fire vanadium trioxide in 800 DEG C when passing into ammonia, then by vanadium trioxide and concentrated sulfuric acid mix and blend, add high purity water and dissolve and filter afterwards, obtain V electrolyte.Gained V electrolyte impurity content Al<17ppm, Na<15ppm, Fe<15ppm, Ca<15ppm, K<10ppm, Cr<5ppm, other impurity contents are all less than 2ppm.
Embodiment 2: the concrete technology of the preparation method of this electrolyte of vanadium redox battery is as described below.
Take ammonium poly-vanadate as raw material, add ammoniacal liquor in case of heating and dissolved, by filtrate adjust ph 7.5, add sodium metaaluminate and carry out removal of impurities.By filtrate adjust ph 1.9 after removal of impurities, add heat sink ammonium poly-vanadate.Then by heavy for ammonium poly-vanadate ammoniacal liquor molten after, adjust ph 2.3 sinks ammonium poly-vanadate, filter, dry after fire vanadium trioxide in 800 DEG C when passing into ammonia, then by vanadium trioxide and concentrated sulfuric acid mix and blend, add high purity water and dissolve and filter afterwards, obtain V electrolyte.Gained V electrolyte impurity content Al<17ppm, Na<15ppm, Fe<15ppm, Ca<15ppm, K<10ppm, Cr<5ppm, other impurity contents are all less than 2ppm.
Embodiment 3: the concrete technology of the preparation method of this electrolyte of vanadium redox battery is as described below.
Be raw material with vanadic oxide, add potassium hydroxide and dissolved, by filtrate adjust ph 8-9, add aluminium chloride and carry out removal of impurities.By filtrate adjust ph 10 after removal of impurities, add heat sink ammonium poly-vanadate.Then by heavy for ammonium poly-vanadate potassium hydroxide molten after, adjust ph 2.3 sinks ammonium poly-vanadate, filter, dry after fire vanadium trioxide in 800 DEG C when passing into ammonia, then by vanadium trioxide and concentrated sulfuric acid mix and blend, add high purity water and dissolve and filter afterwards, obtain V electrolyte.Gained V electrolyte impurity content Al<17ppm, Na<16ppm, Fe<15ppm, Ca<25ppm, K<10ppm, Cr<5ppm, other impurity contents are all less than 2ppm.
Embodiment 4: be raw material with vanadic oxide, adds NaOH and is dissolved, by filtrate adjust ph 10, add aluminum sulfate and carry out removal of impurities.By filtrate adjust ph 2.1 after removal of impurities, add heat sink ammonium poly-vanadate.Then by heavy for ammonium poly-vanadate ammoniacal liquor molten after, adjust ph 3 sinks ammonium poly-vanadate, filter, dry after at 500 DEG C, fire vanadic oxide, then by vanadic oxide vanadium and concentrated sulfuric acid mix and blend, add reducing agent and obtain tetravalence vanadium vanadic sulfate solution.Gained V electrolyte impurity content Si<10ppm, Cr<5ppm, Fe<25ppm, other impurity contents are all less than 10ppm.
Claims (5)
1. the preparation method of a commercial vanadium battery electrolyte, it is characterized in that: will containing vanadium raw materials alkali heavy molten after, adjust ph is precipitation repeatedly, to remove impurity element wherein, then the oxide of vanadium is obtained by roasting, finally by the oxide dissolution of the concentrated sulfuric acid by vanadium, can obtain commercial V electrolyte, its processing step is:
(1) dissolve containing one or more in vanadium raw materials ammonium metavanadate, ammonium poly-vanadate, vanadic oxide, vanadium trioxide with alkali lye, adjust ph 7.5 ~ 10, adds cleaner and carries out removal of impurities; Cleaner is aluminum soluble salt, and described aluminum soluble salt is aluminum sulfate, aluminium chloride or sodium metaaluminate;
(2) the filtrate adjust ph 1.5 ~ 3.0 after removal of impurities, heating precipitation, obtains ammonium poly-vanadate/ammonium metavanadate;
(3), after being dissolved with alkali by ammonium poly-vanadate/ammonium metavanadate, adjust ph 1.5 ~ 3.0, again precipitation, obtain two heavy ammonium poly-vanadate/ammonium metavanadates;
(4) two heavy ammonium poly-vanadate/ammonium metavanadate roastings under reducibility gas, obtain the oxide of vanadium;
(5) oxide of vanadium mixes with the concentrated sulfuric acid, stirring and dissolving, can obtain V electrolyte.
2. the preparation method of commercial vanadium battery electrolyte according to claim 1, is characterized in that: alkali used is the mixture of NaOH, potassium hydroxide, NaOH and potassium hydroxide, ammoniacal liquor, ammonia or liquefied ammonia.
3. the preparation method of commercial vanadium battery electrolyte according to claim 1 and 2, is characterized in that the precipitation process of precipitation process is repeatedly greater than secondary.
4. the preparation method of commercial vanadium battery electrolyte according to claim 1 and 2, is characterized in that: the reducibility gas in described step (4) is hydrogen or ammonia.
5. the preparation method of commercial vanadium battery electrolyte according to claim 1 and 2, is characterized in that: in described step (4), sintering temperature is 500 ~ 800 DEG C.
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104388683B (en) * | 2014-12-08 | 2017-02-22 | 中南大学 | Method for separating and recycling vanadium and chromium from vanadium and chromium-containing material |
| CN104538660B (en) * | 2014-12-25 | 2016-10-19 | 河北钢铁股份有限公司承德分公司 | A kind of high-purity barium oxide preparation method being applicable to all-vanadium flow battery |
| CN105984897B (en) | 2015-01-30 | 2017-05-17 | 中国科学院过程工程研究所 | System and method for producing high-purity vanadium pentoxide powder |
| CN105984900B (en) | 2015-01-30 | 2017-06-13 | 中国科学院过程工程研究所 | A kind of system and method for preparing high purity vanadic anhydride powder |
| CN105984896B (en) | 2015-01-30 | 2017-06-13 | 中国科学院过程工程研究所 | A kind of purification prepares the system and method for high purity vanadic anhydride powder |
| CN105984899B (en) | 2015-01-30 | 2017-05-17 | 中国科学院过程工程研究所 | System and method for purifying vanadium pentoxide |
| CN105984898B (en) | 2015-01-30 | 2017-06-13 | 中国科学院过程工程研究所 | A kind of system and method for producing high-purity vanadium tetraoxide powder |
| CN106257726B (en) * | 2016-01-28 | 2018-03-23 | 中国科学院过程工程研究所 | A kind of system and method for producing high-purity high-activity V electrolyte |
| CN106257725B (en) * | 2016-01-28 | 2018-05-22 | 中国科学院过程工程研究所 | A kind of system and method for preparing the specific valence state electrolyte of high activity all-vanadium flow battery |
| CN106257727B (en) * | 2016-01-28 | 2018-05-22 | 中国科学院过程工程研究所 | A kind of system and method for preparing the high-purity electrolyte of vanadium cell |
| CN106257724B (en) * | 2016-01-28 | 2018-04-24 | 中国科学院过程工程研究所 | A kind of system and method for preparing high-purity V electrolyte |
| CN106257728B (en) * | 2016-01-28 | 2018-01-12 | 中国科学院过程工程研究所 | A kind of system and method for producing the high-purity V electrolyte of 3.5 valencys |
| CN106941186B (en) * | 2017-03-21 | 2019-07-02 | 河钢股份有限公司承德分公司 | A kind of V electrolyte and preparation method thereof |
| CN109136555A (en) * | 2018-08-30 | 2019-01-04 | 东北大学 | Electroreduction produces the oxide precursor of V-Ti and the preparation method of flower ball-shaped ammonium poly-vanadate |
| CN111200149A (en) * | 2018-11-19 | 2020-05-26 | 大连融科储能技术发展有限公司 | Formula and process of electrolyte for all-vanadium redox flow battery |
| CN114180624B (en) * | 2021-12-23 | 2024-01-23 | 大连融科储能集团股份有限公司 | Method for preparing high-purity vanadium by separating ammonium metavanadate raw material vanadium and ammonium |
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| CN100486023C (en) * | 2006-11-01 | 2009-05-06 | 中国科学院金属研究所 | Electrolysis method for preparing all vanadium ion redox flow battery electrolyte |
| CN102468508A (en) * | 2010-11-11 | 2012-05-23 | 中国人民解放军63971部队 | Method for preparing electrolyte of vanadium flow battery |
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Address after: 067102 A block 520, Luanhe town finance square, Shuangluan District, Chengde, Hebei Patentee after: River steel Limited by Share Ltd Chengde branch Address before: 067102 Luanhe town finance square, Shuangluan District, Chengde, Hebei, Hebei iron and steel Limited by Share Ltd Chengde branch Patentee before: Chengde Branch Co., Ltd. of Hebei Iron & Steel Group |