CN102198957A - Method for preparing vanadyl sulfate for vanadium ion redox flow battery - Google Patents
Method for preparing vanadyl sulfate for vanadium ion redox flow battery Download PDFInfo
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- CN102198957A CN102198957A CN2010101404752A CN201010140475A CN102198957A CN 102198957 A CN102198957 A CN 102198957A CN 2010101404752 A CN2010101404752 A CN 2010101404752A CN 201010140475 A CN201010140475 A CN 201010140475A CN 102198957 A CN102198957 A CN 102198957A
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Abstract
The invention provides a method for preparing vanadyl sulfate, comprising the following steps: concentrated sulfuric acid is diluted into dilute sulfuric acid, vanadic anhydride is directly added into the dilute sulfuric acid with stirring to obtain a vanadyl sulfate solution. A reducing agent employed in the invention is selected from one or more of flavanol compounds, anthocyanin compounds, flavonoids, flavonol compounds, phenolic acid compounds and vitamin substances. The preparation method of vanadyl sulfate solves the problems of large consumption of the reducing agent and residues after the reaction in present preparation process, with raising the concentration of vanadyl sulfate and simplifying a technical process.
Description
Technical field
The present invention relates to the electrolytic solution technical field, in particular to a kind of method and application thereof that is used to prepare vanadylic sulfate.
Background technology
All-vanadium flow oxidation reduction cell (all vanadium redox flow battery, VRB) have long service life, charge and discharge system is flexible, and the electric current degree of depth discharges and recharges greatly, plurality of advantages such as no crossed contamination and power loss, the green energy-storing battery that is considered to have most application prospect.As the electrolytic solution of all-vanadium flow oxidation reduction cell core, be subjected to paying close attention to widely.Usually, vanadium cell mainly adopts vanadylic sulfate (VOSO
4) solution is as the electrolytic solution of battery, so the preparation method of vanadylic sulfate and quality directly affect the performance of electrolytic solution.
Usually synthetic by the following technical solutions vanadylic sulfate electrolytic solution: method one, V
2O
5Put into the sulfuric acid heating for dissolving, cooling dilution then adds the reductive agent reduction, the back evaporative crystallization that reacts completely, and dehydration makes VOSO
4Light blue powder.The metal-salt that reductive agent commonly used has oxalic acid, acetate, tartrate, hydrogen sulfide, sulfurous acid or has reductibility.Method two, sulfuric acid mixtures such as electrolysis barium oxide, ammonium vanadate prepare vanadylic sulfate solution, obtain the vanadylic sulfate crystal through condensing crystal.
Yet there is following problem at least in the technical scheme in the above-mentioned correlation technique: if employing method one can only utilize limited several reductive agents with V
2O
5Be reduced into VOSO soluble in water
4, and the concentration of the vanadylic sulfate that makes like this is not high.And owing to use reductive agent, the impurity of being introduced by reductive agent is difficult for removing, and for example, when reductive agent adopted oxalic acid, acetate, tartrate etc., because a little less than this reductive agent reductibility, reagent consumption is big, excessive material was difficult for removing; When reductive agent employing hydrogen sulfide, its reducing property is good, and speed of response is fast, but hydrogen sulfide meltage in water is few, toxicity is big, and contaminate environment also endangers health, when reductive agent adopts sulfurous acid, sulfurous acid instability, solution are overflowed a large amount of sulfurous gas, contaminate environment in reaction process; When the reductive agent employing has the metal-salt of reductibility, then introduce metallic impurity easily, the vanadylic sulfate solution quality that influence makes.In addition, sulfuric acid dissolution V
2O
5Reaction needed under 300 ℃ of high temperature, carry out, so just to the reaction equipment requirements higher.If adopt method two to prepare vanadylic sulfate, then exist the ammonium radical ion to be difficult for removing, problem such as process time is long, and efficient is low.
Because vanadylic sulfate is the electrolytic solution starting material of all-vanadium flow oxidation reduction cell, its preparation technology and preparation method directly have influence on the performance of electrolytic solution, some compositions that wherein in electrolytic solution, exist, as vanadic salts, residue reductive agent electrolytical performance there is bigger influence, especially influences the activity and the long-term cyclical stability of electrolytic solution.Therefore, the industrialization of all-vanadium flow oxidation reduction cell system press for new can low-cost preparation method, processing condition and the new electrolyte formula system that obtains vanadylic sulfate, to adapt to all-vanadium flow oxidation reduction cell low cost, highly active user demand.
Summary of the invention
The present invention aims to provide a kind of method that is used to prepare vanadylic sulfate, utilized a kind of reductive agent among the preparation method that the present invention adopts, this reductive agent is entirely the pure natural product, reducing power is strong, to human body toxicological harmless effect, it is big to solve in the prior art reductive agent consumption, and the residual various pollution problems that cause of reductive agent.And it is not high that preparation method provided by the invention can also solve the vanadylic sulfate concentration of electrolyte that the preparation that exists in the correlation technique draws, the technical process complexity, and the production cost that having relatively high expectations of equipment caused increases problem.
One of purpose of the present invention is to provide a kind of method for preparing vanadylic sulfate solution, and this method comprises: A. is configured to the dilution heat of sulfuric acid of 2.0M-6.0M with the vitriol oil, adds Vanadium Pentoxide in FLAKES while hot in the dilute sulphuric acid that makes, and fully stirs; B. add reductive agent, continue fully to stir, make vanadylic sulfate solution.The concentration of the vanadylic sulfate solution that preferably, makes is 2-4M.
The reductive agent that the present invention adopts, can be selected from flavanols compounds, anthocyanin class compound, flavonoid compound, flavonols compound, phenolic acid compound or the vitamin substances any one or multiple.Lift in the specific embodiment in the present invention, the flavanols compounds of employing can be in training catechin, catechin, l-Epicatechol, the afzelechin any one or multiple; The anthocyanin class compound that adopts can be one or more in Cyanidin, delphinidin, pelargonin, peonidin, the high mallow element; Flavonoid compound can be scutellarin or baicalin, or the mixture of the two; Flavonols can be Quercetin or rutin, or the mixture of the two; Phenolic acid compound be selected from gallic acid, Protocatechuic Acid, the gallic acid any one or multiple; Vitamin substances is selected from the vitamins C or derivatives thereof.
In a specific embodiment of the present invention, described reductive agent is a tea-polyphenol, and wherein the content of catechin is greater than 60% of each composition total amount of tea-polyphenol.
In another specific embodiment of the present invention, described reductive agent is a vitamins C.
In specific embodiment provided by the invention, reductive agent joins in the reaction system with the ratio of weightmeasurement ratio 0.1%～20% in step B.
In the above-mentioned method for preparing vanadylic sulfate solution, when the product that obtains when hope was the vanadylic sulfate powder, the preferred sulfuric acid concentration that adopts was 2-4M; If directly with the vanadylic sulfate solution that makes during as the electrolytic solution of vanadium cell, the vitriolic preferred concentration is 4-6M.
In the method provided by the invention, after step B, can further include: step C, filter the vanadylic sulfate solution that obtains, with the filtrate evaporative crystallization, and step D, slough crystal water, obtain the vanadylic sulfate powder, so just further made the vanadylic sulfate powder.
In method provided by the invention, also the vanadylic sulfate powder that step D can be obtained directly joins in the sulfuric acid, makes different vanadylic sulfate electrolytic solution as required, can be used for the all-vanadium flow oxidation reduction cell.
In addition, can also be by regulating the vitriolic consumption in the process of preparation vanadylic sulfate solution, without vanadylic sulfate powder crystallization process (being above-mentioned steps C, D), directly the vanadylic sulfate solution that step B is obtained is modulated to electrolytic solution, promptly after adding Vanadium Pentoxide in FLAKES, directly the vanadylic sulfate solution that makes is modulated into vanadium electrolytic solution commonly used, the VOSO that for example is mixed with according to practical situation and sulphuric acid soln
4Concentration is at the scope of 1.8-2.5mol/L, H
2SO
4Concentration be the V electrolyte of 3mol/L, be used for the all-vanadium flow oxidation reduction cell.
Another object of the present invention is to provide the vanadylic sulfate solution and the formulated vanadylic sulfate electrolytic solution of sulfuric acid that utilize aforesaid method to make, perhaps vanadylic sulfate powder and the formulated vanadylic sulfate electrolytic solution of sulfuric acid that makes by aforesaid method.
One of purpose of the present invention is reductive agent provided by the invention is applied in the preparation vanadylic sulfate electrolytic solution, by forming the above-mentioned reductive agent of adding in the reaction system at Vanadium Pentoxide in FLAKES and sulfuric acid, make vanadylic sulfate solution, thereby further make vanadylic sulfate electrolytic solution according to demand.
Description of drawings
Accompanying drawing described herein is used to provide further understanding of the present invention, constitutes the application's a part, and illustrative examples of the present invention and explanation thereof are used to explain the present invention, do not constitute improper qualification of the present invention.In the accompanying drawings:
Fig. 1 shows the vanadylic sulfate XRD diffracting spectrum for preparing according to embodiments of the invention 1;
Fig. 2 shows the charge discharge curve for preparing vanadylic sulfate electrolytic solution as the charge discharge curve and the traditional technology of vanadium cell electrolyte according to the preparation vanadylic sulfate of embodiments of the invention 1.
Embodiment
The object of the present invention is to provide a kind of pure natural, non-harmful reductive agent, this reductive agent be selected from flavanol compound, anthocyanin class, flavonoid, flavonols, phenolic acids, the vitamin substances any one or multiple, this reductive agent may be used on preparing in the technology of vanadylic sulfate.
Indication flavanols compounds of the present invention is a kind of natural phant compound, is a subclass of flavonoid material.Content in apple, grape, red wine, tea, cocoa powder and chocolate is very abundant.Flavanols compounds has the molecular structure that proton is provided, and therefore has reductibility.The flavanols compounds that the specific embodiment of the invention adopts can be selected from one or more in training catechin, catechin, l-Epicatechol or the afzelechin.
Anthocyanogen is a cyanidin(e) and the compounds of sugar with the glycosidic link be combined into, is to present a red compounds of group in the flavonoid, extensively is present in the enchylema of flower, fruit, stem, leaf and root organ of plant.The anthocyanin class compound has the molecular structure that proton is provided, and has reductibility.The anthocyanogen that the embodiment of the invention is selected for use can be selected from one or more in Cyanidin, delphinidin, pelargonin, peonidin or the high mallow element.
The compound that flavonoid compound is that a class is present in is natural, have 2-phenyl chromone structure, it in the growth of plant, grow, bloom, aspect such as result and antibiotic diseases prevention, play an important role.There is the cross conjugation system in the flavonoid compound molecule, can in reaction, provides proton, have reductibility.The flavonoid compound that the specific embodiment of the invention is selected for use is scutellarin, baicalin or its mixture.
The flavonols compound is called flavanone kind composition again, is the natural product that nature extensively exists, and is many vegeto-animal important main components, and common flavonol mainly contains ampelopsin, Quercetin and kaempferol.The flavonols compound that the specific embodiment of the invention is selected for use is Quercetin and rutin or its mixture.
Phenolic acid compound (phenolic acid) is meant the compounds that several phenol hydroxyls are arranged on the same phenyl ring.As: coffic acid, chlorogenic acid, gallic acid, gallic acid, Protocatechuic Acid, forulic acid, meson acid etc.Have physiologically active widely,, purposes is widely arranged at aspects such as medicine, agricultural chemicals, cosmetic material and food reductive agents as anti-oxidant, removing free radical, ultra-violet radiation resisting, inhibitory effect and antivirus action.The phenolic acid compound that the embodiment of the invention is selected for use is selected from one or more in gallic acid, Protocatechuic Acid or the gallic acid.
VITAMIN is to keep the essential type organic matter of human life activity, also is the important active substances that keeps HUMAN HEALTH.The VITAMIN that the embodiment of the invention is selected for use can be vitamins C or its derivative, as vitamin C phosphoric ester.
As seen, above material all is present in the natural animals and plants widely, is entirely the chemical ingredients of green non-pollution.These materials all have stronger reductibility because of having unsaturated link(age) in the chemical structural formula.
The method concrete steps that prepare vanadylic sulfate provided by the invention are as follows: A. preparation 2.0-6.0M dilute sulphuric acid, to wherein adding Vanadium Pentoxide in FLAKES, fully stir; B. add reductive agent provided by the invention, be stirred to Vanadium Pentoxide in FLAKES and dissolve fully, obtain vanadylic sulfate solution.Preferably, the vanadylic sulfate strength of solution that makes is 2-4M, so just can be modulated into the vanadylic sulfate electrolytic solution of different concns with the vanadylic sulfate solution that makes and sulfuric acid according to user demand.
The above-mentioned method for preparing vanadylic sulfate solution also can further comprise: step C, and the vanadylic sulfate solution that makes of cooling filters then and gained filtrate is placed on crystallization on the crystal growing furnace; And step D, crystallization is cooled to room temperature, after the washing, obtains the vanadylic sulfate crystal powder by centrifugal or additive method.
In the specific embodiment provided by the invention, reductive agent all joins in the reaction system with the ratio of weightmeasurement ratio (g/ml) 0.1%～20%, but those skilled in the art fully can be according to the reductibility of reductive agent, with different weightmeasurement ratios it is added in the reaction soln, make vanadylic sulfate solution.
In above-mentioned preparation vanadylic sulfate solution methods, the concentration of dilute sulphuric acid is 2.0-6.0M.When the final product that obtains when hope was the vanadylic sulfate powder, preferred sulfuric acid concentration was 2-4M, otherwise unnecessary acid is difficult for removing.When the vanadylic sulfate solution that makes directly as the V electrolyte time spent, optimum sulfuric acid concentration is 4-6M.
As seen, when products obtained therefrom of the present invention is used as the all-vanadium redox flow battery electrolyte raw material, both can be chosen in the vanadylic sulfate powder that dissolving step D obtains in the sulphuric acid soln, make corresponding vanadylic sulfate electrolytic solution, also can be by regulating the sulfuric acid consumption, without vanadylic sulfate powder crystallization process, vanadylic sulfate solution modulation the becoming electrolytic solution that directly step B is obtained: be about to vanadylic sulfate solution that step B obtains directly and the ultimate density that is modulated into as required of sulfuric acid carry out proportioning, such as with VOSO
4Content is allocated in the scope of 1.8-2.5M, H
2SO
4Be allocated as 3M, make corresponding vanadylic sulfate electrolytic solution.
The principal reaction equation is:
1.V
2O
5+H
2SO
4＝(VO
2)
2SO
4+H
2O
2. (VO
2)
2SO
4+ H
2O+2H
+(reductive agent)=2VOSO
4+ 2H
2O
The plant and instrument that adopts: crystal growing furnace, pH pH-value determination pH instrument, whizzer, LAND charge-discharge test instrument.
The raw material that adopts: Vanadium Pentoxide in FLAKES, oxalic acid, the vitriol oil, training catechin, catechin, l-Epicatechol, afzelechin, Cyanidin, delphinidin, pelargonin, peonidin, high mallow element, scutellarin, baicalin, Quercetin, rutin, gallic acid, Protocatechuic Acid, gallic acid, vitamins C, ascorbic acid phosphoric acid esters are all purchased from commerce, purity is analytical pure, and the content of catechin is greater than 60% in the tea-polyphenol.
Comparative example
The technological line of existing synthetic vanadylic sulfate is: add sulfuric acid in the Vanadium Pentoxide in FLAKES, and heating for dissolving, the cooling dilution adds reductive agent reduction such as oxalic acid or sulfurous acid, and the evaporative crystallization dehydration generates the light blue powder of vanadylic sulfate.
Principal reaction equation: V
2O
5+ H
2SO
4=(VO
2)
2SO
4+ H
2O
Make reductive agent with oxalic acid: (VO
2)
2SO
4+ H
2C
2O
4+ H
2SO
4=2VOSO
4+ 2CO
2+ 2H
2O
Or make reductive agent: (VO with sulfurous acid
2)
2SO
4+ H
2SO
3=2VOSO
4+ H
2O
Concrete implementation step is as follows: in concentration is among the aqueous sulfuric acid 350mL of 3mol/L, adds Vanadium Pentoxide in FLAKES 65g, and heating is also stirred, and temperature is 80 ℃-100 ℃, it is dissolved fully after, the cooling dilution, add oxalic acid 0.2mol after, reacted 10 hours.Behind above-mentioned reacting liquid filtering, be placed on crystallization on the crystal growing furnace, obtain blue powder.
It below is the specific embodiment of the invention.The vitriol oil can be made into the concentration of 2-6M,, make that the vanadium concentration in the system of reaction back reaches 2-4M to wherein adding Vanadium Pentoxide in FLAKES (concrete quality will according to volume calculation).In the preferred case, also sulfuric acid can be made into the concentration of 4-6M,, make that the vanadium concentration in the system of reaction back reaches 2-4M to wherein adding Vanadium Pentoxide in FLAKES.
Embodiment 1:
With 1: 3 dilution proportion vitriol oil, the sulphuric acid soln of preparation 300mL was when the dilution heat that the vitriol oil discharged adds 73g V
2O
5, after fully stirring, add tea-polyphenol 10g, and constantly be stirred to V
2O
5Dissolving fully, cooled and filtered, the blue vanadylic sulfate solution that obtains, after tested: pH is 1.0-1.3, vanadium concentration is 2.7mol/L.Filtrate is placed on crystallization on the crystal growing furnace (80 ℃ of temperature controls) the sand-like crystalline powder of au bleu, is being cooled to room temperature, and with the 200ml washing with acetone, obtain the vanadylic sulfate crystal, tetravalence content of vanadium 98.6%, yield 96% after centrifugal.
The vanadylic sulfate powder that obtains is carried out thing detect mutually, draw vanadylic sulfate thing phasor, as shown in Figure 1.
The vanadylic sulfate crystal that obtains is mixed with 1.8M VOSO
4+ 3M H
2SO
4Solution, as electrolyte for vanadium cell, inject the positive and negative electrode retort respectively, carry out charge-discharge test, the result who obtains is as shown in Figure 2.Current density is 50mAcm
-2Fill entirely and put entirely under the test condition, the charging/discharging voltage platform of test battery is steady, and threshold voltage is about 1.25V in the discharge, and loading capacity approaches theoretical loading capacity, has better electrochemical performance.
Embodiment 2:
Take by weighing 150.0g V
2O
5In 600.0mL concentration is 5.0molL
-1Sulphuric acid soln in, add vitamins C 40g, be stirred to V
2O
5Dissolving fully, final vanadium concentration is 2.75mol/L, cooled and filtered, the blue vanadylic sulfate solution that obtains, the blue vanadylic sulfate solution that obtains is directly added vitriol oil 80ml, and deionized water is diluted to 800ml, as all-vanadium flow oxidation reduction cell vanadylic sulfate electrolytic solution.Anodal 100ml, negative pole 50ml carries out the dynamic battery charge-discharge test, adopts electrochemical workstation to carry out electro-chemical test simultaneously.
Simultaneously with the vanadylic sulfate electrolytic solution that makes as negative pole electrolytic solution, the equal-volume H of same ion concentration
2SO
4Solution is anodal electrolytic solution, places respectively in the electrolyzer that separates with ion-exchange membrane (can be cationic exchange membrane as: perfluoro sulfonic acid membrane also can be anion-exchange membrane).With the stereotype is electrode, is 80mAcm in current density
-2Current density under electrolysis, by detecting the control of Electric potentials electrolysis terminal point of electrolytic solution, terminal point current potential 150-250mV obtains vanadium ion concentration 〉=1.8molL
-1All-vanadium flow oxidation reduction cell positive and negative electrode V
3+/ V
4+Electrolytic solution.
With the electrolytic solution that obtains at 50mAcm
-2Fill entirely under the current density and put test entirely, firing potential is 1.376V, energy efficiency 78.24%, voltage efficiency is that 81.5% current efficiency is 96%, the charging/discharging voltage platform of test battery is steady, and threshold voltage has better electrochemical performance in the discharge about 1.26V.
Embodiment 3
Take by weighing 72.7g V
2O
5In 400.0mL concentration is 2.0molL
-1Sulphuric acid soln in, after fully stirring, add reductive agent 0.4g, the composition proportion of reductive agent is as shown in table 1; Be stirred to V
2O
5Dissolving fully, vanadium concentration is 2.0mol/L, cooled and filtered, the blue vanadylic sulfate solution that obtains is placed on crystallization on the crystal growing furnace (80 ℃ of temperature controls) the sand-like crystalline powder of au bleu with filtrate, is cooled to room temperature again, and with the 200ml washing with acetone, drying obtains the vanadylic sulfate powder.
Method according to embodiment 1 is mixed with 2.0MVOSO with the vanadylic sulfate crystal that obtains
4+ 3M H
2SO
4Vanadylic sulfate electrolytic solution, and carry out corresponding electrically test, the result is as shown in table 2.
Embodiment 4
Take by weighing 68.2g V
2O
5In 250.0mL concentration is 6.0molL
-1Sulphuric acid soln in, add reductive agent 12.5g, the composition proportion of reductive agent is as shown in table 1; Be stirred to V
2O
5Dissolving fully, vanadium concentration is 3.0mol/L, cooled and filtered, the blue vanadylic sulfate solution that obtains according to the method for embodiment 2, adds deionized water and is diluted to 420ml, makes vanadylic sulfate electrolytic solution, and carries out corresponding electrically test, and the result is as shown in table 2.
Embodiment 5
Take by weighing 68.2g V
2O
5In 300.0mL concentration is 3.0molL
-1Sulphuric acid soln in, add reductive agent 30g, the composition proportion of reductive agent is as shown in table 1; Be stirred to V
2O
5Dissolving fully, vanadium concentration is 2.5mol/L, cooled and filtered, the blue vanadylic sulfate solution that obtains is placed on crystallization on the crystal growing furnace (80 ℃ of temperature controls) the sand-like crystalline powder of au bleu with filtrate, is cooled to room temperature again, and with the 200ml washing with acetone, drying obtains the vanadylic sulfate powder.
Method according to embodiment 1 is mixed with 2.0MVOSO with the vanadylic sulfate crystal that obtains
4+ 3M H
2SO
4Vanadylic sulfate electrolytic solution, and carry out corresponding electrically test, the result is as shown in table 2.
Embodiment 6
Take by weighing 127.3g V
2O
5In 400.0mL concentration is 3.5mol.L
-1Sulphuric acid soln in, add reductive agent 80g, the composition proportion of reductive agent is as shown in table 1; Be stirred to V
2O
5Dissolving fully, vanadium concentration is 3.5mol/L, cooled and filtered, the blue vanadylic sulfate solution that obtains is placed on crystallization on the crystal growing furnace (80 ℃ of temperature controls) the sand-like crystalline powder of au bleu with filtrate, is cooled to room temperature again, and with the 200ml washing with acetone, drying obtains the vanadylic sulfate powder.
Method according to embodiment 1 is mixed with 2.0MVOSO with the vanadylic sulfate crystal that obtains
4+ 3M H
2SO
4Vanadylic sulfate electrolytic solution, and carry out corresponding electrically test, the result is as shown in table 2.
Embodiment 7
Take by weighing 182g V
2O
5In 500.0mL concentration is 5.5molL
-1Sulphuric acid soln in, add reductive agent 40g, the composition proportion of reductive agent is as shown in table 1; Be stirred to V
2O
5Dissolving fully, vanadium concentration is 4.0mol/L, cooled and filtered, the blue vanadylic sulfate solution that obtains, according to the method for embodiment 2, add the 50ml vitriol oil, deionized water is diluted to 1000mL, make vanadylic sulfate electrolytic solution, and carry out corresponding electrically test, the result is as shown in table 2.
Embodiment 8
Take by weighing 109g V
2O
5In 400.0mL concentration is 2.5molL
-1Sulphuric acid soln in, add reductive agent 16g, the composition proportion of reductive agent is as shown in table 1; Be stirred to V
2O
5Dissolving fully, vanadium concentration is 3.0mol/L, cooled and filtered, the blue vanadylic sulfate solution that obtains is placed on crystallization on the crystal growing furnace (80 ℃ of temperature controls) the sand-like crystalline powder of au bleu with filtrate, is cooled to room temperature again, and with the 200ml washing with acetone, drying obtains the vanadylic sulfate powder.
Make vanadylic sulfate electrolytic solution according to the method for embodiment 1, and carry out corresponding electrically test, the result is as shown in table 2.
Embodiment 9
Take by weighing 60g V
2O
5In 300.0mL concentration is 4.0molL
-1Aqueous sulfuric acid in, add reductive agent 36g, the composition proportion of reductive agent is as shown in table 1; Be stirred to V
2O
5Dissolving fully, vanadium concentration is 2.2mol/L, cooled and filtered, the blue vanadylic sulfate solution that obtains is placed on crystallization on the crystal growing furnace (80 ℃ of temperature controls) the sand-like crystalline powder of au bleu with filtrate, is cooled to room temperature again, and with the 200ml washing with acetone, drying obtains the vanadylic sulfate powder.
Method according to embodiment 1 is mixed with 1.8MVOSO with the vanadylic sulfate crystal that obtains
4+ 3M H
2SO
4Vanadylic sulfate electrolytic solution is made vanadylic sulfate electrolytic solution, and carries out corresponding electrically test, and the result is as shown in table 2.
The one-tenth that table 1 embodiment 3-9 makes reductive agent is grouped into
Table 2 comparative example and embodiment 1-9 gained vanadylic sulfate electrolytic solution discharge and recharge experimental result
| Firing potential (V) | Energy efficiency | Voltage efficiency | Current efficiency | Threshold voltage in the discharge (V) | |
| Comparative example | 1.32 | 70％ | 76％ | 92％ | 1.25 |
| Embodiment 1 | 1.391 | 78.8％ | 83％ | 95％ | 1.28 |
| Embodiment 2 | 1.376 | 78.24％ | 81.5％ | 96％ | 1.26 |
| Embodiment 3 | 1.375 | 76.48％ | 80.5％ | 95％ | 1.27 |
| Embodiment 4 | 1.384 | 76.14％ | 81％ | 94％ | 1.26 |
| Embodiment 5 | 1.376 | 77.08％ | 82％ | 94％ | 1.26 |
| Embodiment 6 | 1.390 | 76.95％ | 81％ | 95％ | 1.26 |
| Embodiment 7 | 1.373 | 79.20％ | 82.5％ | 96％ | 1.26 |
| Embodiment 8 | 1.370 | 78.4％ | 80.0％ | 95％ | 1.28 |
| Embodiment 9 | 1.381 | 77.9％ | 82.0％ | 95％ | 1.28 |
Discharge and recharge experimental result as can be known by embodiment 1-9 and comparative example gained vanadylic sulfate electrolytic solution among the table 1-2, the electrolyte property that obtains according to embodiments of the invention is good, can satisfy the every requirement in the practical application.
As can be seen from the above description, the above embodiments of the present invention have realized following technique effect:
1, reductive agent reductibility provided by the invention is strong, need not a large amount of addings; And, this reductive agent is the green non-pollution reductive agent, the all the components that adopts is and extensively is present in natural nontoxic chemical ingredients, has the eco-friendly characteristic of using than prior art of reductive agents such as sulfurous gas, quickened the dissolving of Vanadium Pentoxide in FLAKES in acidic solution simultaneously, increased substantially the preparation efficiency of vanadylic sulfate, and this reductive agent can not introduce other impurity, the concentration of the vanadylic sulfate solution that makes is higher;
2, the method for preparing vanadylic sulfate provided by the invention, by in the dilute sulphuric acid of the 2M-6.0M concentration for preparing, adding Vanadium Pentoxide in FLAKES, add reductive agent again, utilize the Heat of fusion initiation reaction, obtain vanadylic sulfate solution, thereby, solved under the high temperature and reacted, the equipment requirements problem of higher.And preparation method of the present invention has omitted steps such as heating, the reaction conditions gentleness, and technology is simple, so this method effectively reduces production cost, has improved production efficiency;
3, the vanadylic sulfate solution that obtains in the preparation process can obtain vanadylic sulfate electrolytic solution by adding forms such as acid modulation, and this electrolytic solution can be directly used in all-vanadium flow battery; Once preparation reaches the vanadylic sulfate solution compolision unanimity that dissolution process obtains again, and is easy to use; Particularly with the Vanadosulfuric acid crystal of preparation through peracidity dissolution process again, obtain and the identical solution of ortho-sulfuric acid vanadyl mother liquor composition, especially be suitable for the all-vanadium flow oxidation reduction cell.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a method for preparing vanadylic sulfate solution is characterized in that, comprising:
A, diluting concentrated sulfuric acid is become the dilute sulphuric acid of 2-6M, in described dilute sulphuric acid, add Vanadium Pentoxide in FLAKES, and fully stir;
B, adding reductive agent fully stir and make described vanadylic sulfate solution;
Wherein, described reductive agent be selected from flavanols compounds, anthocyanin class compound, flavonoid compound, flavonols compound, phenolic acid compound, the vitamin substances any one or multiple.
2. method according to claim 1 is characterized in that, described flavanols compounds be selected from training catechin, catechin, l-Epicatechol, the afzelechin any one or multiple; Described anthocyanin class compound be selected from Cyanidin, delphinidin, pelargonin, peonidin, the high mallow element any one or multiple; Described flavonoid compound be selected from dried orange peel glycosides, the Liquiritigenin any one or multiple; Described flavonols be selected from Quercetin, the rutin any one or multiple; Described phenolic acid compound be selected from gallic acid, Protocatechuic Acid, P-hydroxybenzoic acid, vanillic acid, o-methoxybenzoic acid, forulic acid, phenylformic acid, Whitfield's ointment, the gallic acid any one or multiple; Described vitamin substances is selected from the vitamins C or derivatives thereof.
3. method according to claim 1 is characterized in that described reductive agent is a tea-polyphenol, and wherein, the content of catechin is greater than 60% in the described tea-polyphenol.
4. method according to claim 1 is characterized in that described reductive agent is a vitamins C.
5. according to each described method among the claim 1-4, it is characterized in that described reductive agent adds reaction system according to the ratio of weightmeasurement ratio 0.1%-20%.
6. method according to claim 1 is characterized in that, further comprises step C and D:
C. filter described vanadylic sulfate solution, with the filtrate evaporative crystallization;
D. slough crystal water, obtain the vanadylic sulfate powder.
7. vanadylic sulfate solution and sulfuric acid vanadylic sulfate powder formulated or that claim 6 makes and formulated vanadylic sulfate electrolytic solution of sulfuric acid that utilizes each described method of claim 1-4 to make.
8. the application of reductive agent in preparation vanadylic sulfate electrolytic solution, it is characterized in that, described reductive agent be selected from flavanols compounds, anthocyanin class compound, flavonoid compound, flavonols compound, phenolic acid compound, the vitamin substances any one or multiple.
9. application according to claim 8 is characterized in that, described flavanols compounds be selected from training catechin, catechin, l-Epicatechol, the afzelechin any one or multiple; Described anthocyanin class compound be selected from Cyanidin, delphinidin, pelargonin, peonidin, the high mallow element any one or multiple; Described flavonoid compound be selected from dried orange peel glycosides, the Liquiritigenin any one or multiple; Described flavonols be selected from Quercetin, the rutin any one or multiple; Described phenolic acid compound be selected from gallic acid, Protocatechuic Acid, P-hydroxybenzoic acid, vanillic acid, o-methoxybenzoic acid, forulic acid, phenylformic acid, Whitfield's ointment, the gallic acid any one or multiple; Described vitamin substances is selected from the vitamins C or derivatives thereof.
10. according to Claim 8 or 9 described application, it is characterized in that, Vanadium Pentoxide in FLAKES is added after sulfuric acid forms reaction system, described reductive agent is joined described reaction system.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102683733A (en) * | 2012-04-12 | 2012-09-19 | 广州有色金属研究院 | Preparation method for vanadyl sulfate electrolyte of all-vanadium flow battery |
| CN103193268A (en) * | 2013-04-01 | 2013-07-10 | 胡国良 | Preparation method of vanadyl sulfate for vanadium cell |
| CN103303976A (en) * | 2013-06-04 | 2013-09-18 | 青岛清阳新材料发展有限公司 | Preparation method of active substance, vanadyl sulfate, of vanadium battery |
| CN103420415A (en) * | 2012-05-15 | 2013-12-04 | 攀钢集团攀枝花钢钒有限公司 | Preparation method of vanadyl sulfate |
| CN103441295A (en) * | 2013-09-02 | 2013-12-11 | 许伟琦 | Method for preparing electrolyte of vanadium redox battery |
| CN106395900A (en) * | 2016-11-11 | 2017-02-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for removing impurities in vanadyl sulfate crystal |
| CN110404498A (en) * | 2019-09-02 | 2019-11-05 | 四川星明能源环保科技有限公司 | A kind of oxygen vanadium sulphate solution method for controlling reaction temperature and preparation facilities |
| CN110970646A (en) * | 2018-09-29 | 2020-04-07 | 中国科学院大连化学物理研究所 | Application of additive in negative electrode electrolyte of all-vanadium redox flow battery |
| US10749168B1 (en) | 2018-06-19 | 2020-08-18 | Michael E. Johnson | Electrochemical cell or battery |
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| CN101651221A (en) * | 2009-09-27 | 2010-02-17 | 湖南维邦新能源有限公司 | Method for preparing electrolyte for vanadium cell |
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| CN102683733B (en) * | 2012-04-12 | 2014-07-09 | 广州有色金属研究院 | Preparation method for vanadyl sulfate electrolyte of all-vanadium flow battery |
| CN102683733A (en) * | 2012-04-12 | 2012-09-19 | 广州有色金属研究院 | Preparation method for vanadyl sulfate electrolyte of all-vanadium flow battery |
| CN103420415B (en) * | 2012-05-15 | 2015-12-02 | 攀钢集团攀枝花钢钒有限公司 | A kind of preparation method of vanadylic sulfate |
| CN103420415A (en) * | 2012-05-15 | 2013-12-04 | 攀钢集团攀枝花钢钒有限公司 | Preparation method of vanadyl sulfate |
| CN103193268A (en) * | 2013-04-01 | 2013-07-10 | 胡国良 | Preparation method of vanadyl sulfate for vanadium cell |
| CN103303976A (en) * | 2013-06-04 | 2013-09-18 | 青岛清阳新材料发展有限公司 | Preparation method of active substance, vanadyl sulfate, of vanadium battery |
| CN103441295A (en) * | 2013-09-02 | 2013-12-11 | 许伟琦 | Method for preparing electrolyte of vanadium redox battery |
| CN106395900A (en) * | 2016-11-11 | 2017-02-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for removing impurities in vanadyl sulfate crystal |
| CN106395900B (en) * | 2016-11-11 | 2018-04-24 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of method of impurity in removal oxygen vanadium sulfate crystals |
| US10749168B1 (en) | 2018-06-19 | 2020-08-18 | Michael E. Johnson | Electrochemical cell or battery |
| CN110970646A (en) * | 2018-09-29 | 2020-04-07 | 中国科学院大连化学物理研究所 | Application of additive in negative electrode electrolyte of all-vanadium redox flow battery |
| CN110970646B (en) * | 2018-09-29 | 2021-06-25 | 中国科学院大连化学物理研究所 | Application of additive in negative electrode electrolyte of all-vanadium redox flow battery |
| CN110404498A (en) * | 2019-09-02 | 2019-11-05 | 四川星明能源环保科技有限公司 | A kind of oxygen vanadium sulphate solution method for controlling reaction temperature and preparation facilities |
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