CN104037439A - Combined chemical-electrochemical method for preparing vanadium redox flow battery electrolyte - Google Patents
Combined chemical-electrochemical method for preparing vanadium redox flow battery electrolyte Download PDFInfo
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Abstract
The invention relates to a combined chemical-electrochemical method for preparing an all-vanadium redox flow battery electrolyte. The method adopts a solid or solution containing soluble vanadate, especially vanadium slag leachate obtained after steel-making with vanadic titano-magnetite, for production of a high-purity high-concentration vanadium electrolyte. The method is characterized in that a vanadyl sulfate electrolyte with a sulfuric acid concentration of 1 to 6 mol/L and a vanadium concentration of 1 to 5 mol/L can be prepared through impurity removal, acidic vanadium precipitation, multiple alkaline leaching and vanadium precipitation, calcination and reduction, an electrochemical process is cooperatively used so as to prepare a 3.5-valent or 3-valent vanadium electrolyte, and after electrolysis, the vanadium electrolyte of a positive electrode can be repeatedly used through chemical reduction. The method provided by the invention can treat the vanadium slag leachate and the solid or solution containing soluble vanadate and has the advantages of simple process flow, mild reaction conditions, substantially reduced cost, etc.; and the prepared high-purity high-concentration vanadium electrolyte is especially applicable to an all-vanadium redox flow battery.
Description
Technical field
The present invention relates to a kind of processing and manufacturing technology and electrochemistry preparation field of all-vanadium redox flow battery electrolyte, particularly a kind ofly produce electrolyte used for all-vanadium redox flow battery preparation method by vanadium slag leachate or containing the solid of soluble vanadium hydrochlorate or solution.
Background technology
All-vanadium flow battery (VRB) active material is the same element that invertibity is appraised at the current rate preferably, the cross pollution of positive/negative solution is down to minimum on the impact of battery performance, and is beneficial to the regeneration of electrolyte after long-time running.Therefore, in existing liquid energy-storage technology, all-vanadium flow battery is generally had an optimistic view of, and its unique advantage and successfully example have shown wide application prospect on energy storage market.
The active material of all-vanadium flow battery is dissolved in electrolyte, and therefore, electrolyte is its core.For improving energy density and the useful life of battery, electrolyte solution should have high concentration, requires to have again high stability.How efficiently, the V electrolyte of preparing at low cost high concentration, high stability is the major issue of restriction all-vanadium flow battery scale application.The technology of preparing of existing V electrolyte is mainly divided into chemical method and electrochemical electrolysis method.Chemical method adopts V mostly
2o
5or V
2o
3for raw material, in sulfuric acid solution, use SO
2, the reducing agent reduction such as S powder, organic acid, alcohol, aldehyde, or V
2o
5and V
2o
3self-catalyzed reaction, adjusts vanadium concentration after reacting completely, add suitable additive, is placed in electrolysis tank electrolysis, makes the electrolyte for all-vanadium flow battery.In above-mentioned technology, use V
2o
5and V
2o
3cost of material high, and also high to equipment requirement.Electrochemical electrolysis reducing process is prepared electrolyte, general electroreduction V
2o
5, NH
4vO
3or V
2o
5and V
2o
3the sulfuric acid solution of mixture, adopts the sodium sulphate H that adds same ion intensity to electrode
2sO
4solution; Taking the high stereotype of overpotential of hydrogen evolution as electrode or DSA electrode or catalysis analyse oxygen electrode as anode, graphite cake is negative pole; Anode is analysed oxygen side reaction, and the reduction of negative electrode generation pentavalent vanadium makes the V electrolyte of 4 valencys, 3 valencys or 3.5 valencys.The plumbous plate electrode of the method, voltage is high, and energy consumption is large, Oxygen anodic evolution corrosion, and terminal control is more difficult, and vanadium ion seepage loss is serious, is not suitable for the large-scale production of electrolyte.More common technology is mixed dissolution in sulfuric acid solution by vanadic oxide and vanadium trioxide, carries out chemistry and electrochemical reduction, and preparation becomes trivalent and tetravalence V electrolyte.This technology is with the defect of above-mentioned electronation and electrochemical reduction.For the problem of avoiding electrolytic preparation 3.5 valency V electrolytes to exist, have V
2o
3mix with sulfuric acid, at the temperature lower calcination of 100～300 DEG C, part trivalent vanadium is oxidized into tetravalence with air, obtain trivalent and tetravalence vanadium respectively accounts for 50% mixture, the method is difficult to control to the degree of air oxidation.Or with V
2o
5or V
2o
3for raw material makes VOSO
4, use not reducibility gas CO or the H of sulfur-bearing
23.5 valency V electrolytes are prepared in partial reduction.Similarly, the method is wayward by the degree of gas reduction, and toxicity and danger higher.
For reducing costs, also having the vanadium factory intermediate liquid of similar this patent of employing or the vanadium solution that the water logging of basic roasting stone coal mine obtains is raw material, in acid solution, is reduced to tetravalence vanadium with liquid sulfur dioxide, is 4 left and right more subsequently with sodium carbonate adjust pH, acquisition VO
2precipitation.VO
2precipitate with after sulfuric acid dissolution the V electrolyte of electrolytic preparation 3.5 valencys.The problem of this technology path is mainly the VO of gained
2for colloidal precipitation, be mingled with morely, vanadium extraction rate is on the low side, has affected the purity of end product-V electrolyte.Kunming University of Science and Technology obtains bone coal acidleach reduction the leachate of tetravalence vanadium, directly obtain the tetravalence vanadium V electrolyte of variable concentrations through extraction and sulfuric acid solution reextraction, the method removal of impurity is not high, and electrolyte is difficult to avoid carrying secretly organic extractant, must can be used for vanadium cell by the organic substance of carrying secretly in the Adsorption electrolyte such as active carbon, the cost of preparation increases.
The present invention adopts cheap vanadium slag leachate-sodium vanadate solution raw material, adopt removal of impurities-precipitation-alkali lye embathe-calcine-reduce-electrolysis six steps prepare the required high-purity high concentration positive/negative V electrolyte of all-vanadium flow battery.This method adopts removal of impurities, precipitation, multistage alkali lye to embathe the simple chemical settling of three steps and suddenly can effectively remove impurity.Wherein removal of impurities one step can be by impurity such as the silicate of more difficult removal, Ca and Cr; Precipitation one step can obtain the lenticular ammonium metavanadate that purity is higher; Embathe and can obtain highly purified ammonium metavanadate sediment by multistage alkali lye.Soluble reducing agent used is cheap and have a high chemism.The similar all-vanadium flow battery of electrolyser construction used, the moon/anode all adopts vanadium solution, has effectively suppressed the infiltration of the negative electrode vanadium solution anode of electroreduction, and the inexpensive porous carbon felt of high activity that electrode material also can be continued to use former all-vanadium flow battery is electrode.Combine with electrolysis by electronation, realized reusing with the scale of negative electrode V electrolyte of anode vanadium solution and prepared.This method technique is simple, not high to equipment requirement, and raw material, reagent in preparation process are all comparatively cheap, and the impurity such as silicate can conveniently remove, and is suitable for large-scale production preparation.
Summary of the invention
The object of the invention is to utilize the middle liquid-solid of ore vanadium extraction or liquid sodium vanadate is raw material, provides a kind of mode that adopts chemistry to combine with electrolysis to prepare the method for all-vanadium redox flow battery electrolyte.The method has the advantages such as technology and equipment is simple, easy and simple to handle, purity is controlled, the remarkable reduction of preparation cost.
The object of the invention is to realize by following method, chemical method of being combined vanadium redox flow battery electrolyte processed with electrochemistry comprises the following steps:
(1) adopt vanadium slag leachate or containing the solid of soluble vanadium hydrochlorate or solution as raw material, adjust pH be alkalescence, adds cleaner, makes the impurity of the more high-leveled and difficult removal of content in vanadate solution form precipitation, filters removal;
(2) by vanadate solution adjust pH to 4～6 through preliminary removal of impurities of step (1) gained, add precipitation agent-sulfuric acid money, ammonium acetate, ammonium chloride or Ammonia, the mol ratio of the material of precipitation agent and vanadium is 1: 1～4: 1, carry out precipitation reaction, precipitation reaction temperature is 90～100 DEG C, reaction time is 0.5～3 hour, forms ammonium vanadate crystal settling, removes most of impurity;
(3) the ammonium vanadate sediment obtaining in step (2) is put into pure water, be heated with stirring to 80 DEG C, add ammoniacal liquor adjust pH is 8～10 simultaneously, fully stirs after 2 hours, static cooling, filters, and obtains the vanadic acid money of one-level purifying;
(4) repeating step (3), can obtain the ammonium vanadate of multistage purifying;
(5) ammonium vanadate step (4) being obtained is calcined at 400～650 DEG C, and the time is 0.5～5 hour, obtains high-purity vanadic oxide;
(6) in sulfuric acid medium, step (2) high-purity vanadic oxide that obtains is reduced to tetravalence vanadium solution with soluble reducing agent, obtain the anode electrolyte for all-vanadium flow battery;
(7) the moon/anode that isopyknic tetravalence vanadium solution is placed in to electrolytic cell group carries out constant-potential electrolysis, and negative electrode obtains the trivalent vanadium electrolyte for all-vanadium flow battery negative pole; In the pentavalent vanadium solution that anode obtains, add soluble reducing agent, be converted into tetravalence vanadium solution; Isocyatic equal-volume trivalent vanadium solution and tetravalence vanadium solution are mixed, obtain all 3.5 valency V electrolytes of use of all-vanadium flow battery positive and negative electrode.
Vanadium slag leachate of the present invention or soluble vanadium hydrochlorate are the alkali metal salt of vanadic acid, metavanadic acid, pyrovanadic acid or their mixture, and concentration is 0.5～50g/L; Cleaner is aluminium salt, magnesium salts and calcium salt, is 8～9 o'clock in pH value, removes silicate, chromate, phosphate radical anion in vanadate solution; PH is 10～12 o'clock, with the metal cation in cleaner-carbonate and sulfide removal vanadate solution.
The mol ratio of the material of cleaner aluminium salt of the present invention and material liquid mesosilicic acid root is 1: 1～1.5: 1; In cleaner magnesium salts and material liquid, the mol ratio of the material of chromate is 1: 1～1.5: 1; In cleaner calcium salt and material liquid, the mol ratio of the material of phosphate radical is 0.9: 1～1.5: 1.In cleaner carbonate and material liquid, the mol ratio of the material of Ca or Mg ion is 0.9: 1～1.5: 1; In cleaner sulfide and material liquid, the mol ratio of the material of Ca or Cd ion is 0.8: 1～1.2: 1.
Soluble reducing agent of the present invention is hydrazine, hydrazine sulfate, phenylhydrazine, phenylhydrazine sulfate, hydroxylammonium, HAS, diamine, hydrazine sulfate or their mixture.
The molar ratio of soluble reducing agent of the present invention and vanadate or pentavalent barium oxide is the betatopic molal quantity of soluble reducing agent: the molal quantity of pentavalent vanadium is 1～8 times of the variable valence mumber inverse of soluble reducing agent.
Electrolysis unit of the present invention comprises: electrolytic cell group, negative electrode fluid reservoir, anode fluid reservoir, liquid transmission pipeline and pump, electrolytic cell group is made up of more than 1 or 1 electrolytic cell, electrolytic cell quantity can be determined according to the daily output of electrolytic preparation V electrolyte, and negative electrode fluid reservoir is connected with the negative electrode of electrolytic cell group by liquid transmission pipeline through pump; Anode fluid reservoir is connected with the anode of electrolytic cell group by liquid transmission pipeline through pump; The collector plate of electrolytic cell is the composite plate of graphite cake, conducting polymer and the graphite of seepage-proof liquid densification, and negative electrode and anode material are porous carbon felt, porous graphite felt or porous carbon fiber.Barrier film between the moon/anode is cation-exchange membrane, anion-exchange membrane or anion/cation exchange composite membrane.Electrolytic parameter is: constant-potential electrolysis mode, and the voltage between the moon/positive electrode is 1.7V; By detecting Current Control electrolysis terminal, terminal electric current is 10～80mA.
In the prepared high purity vanadium electrolyte of the present invention, except v element and potassium, sodium, other metal impurities ion concentrations in electrolyte are all below 10ppm.
The invention has the beneficial effects as follows that raw material, reagent in preparation process are cheap, the simple and easy convenient operation of technical process, and it is high to make product purity, easily accomplishes scale production.
Brief description of the drawings
Fig. 1 all-vanadium redox flow battery electrolyte preparation flow sketch
The electrolysis unit schematic diagram of 2 electrolytic cell compositions of Fig. 2
In figure: 1. pump, 2. anode fluid reservoir, 3. negative electrode fluid reservoir, 4. pipeline, 5. end plate, 6. anode graphite felt electrode, 7. amberplex, 8. anode, 9. negative electrode, 10. collector plate, 11. negative electrode graphite felt electrodes.
Embodiment
Embodiment 1
Get 5000 milliliters of NaVO containing vanadium 0.4M
3solution, regulator solution pH value is 9, adds aluminum sulfate (according to Si: Al=1: 1.2 mol ratio), leaves standstill 12h, filtering-depositing after adding thermal agitation 2h.In filtrate according to Ca: CO
3 2-=1: 1 mol ratio adds sodium carbonate, and regulating the pH value of filtrate is 10, and Slow cooling after ebuillition of heated leaves standstill 12h, sedimentation and filtration.In reactor, add above-mentioned NaVO after preliminary impurity and purification
3solution, regulator solution acidity to pH value is 5, according to NH
4 +: V=1: 3 mol ratio adds ammonium chloride, stir after 1h, the pH=2 of regulator solution stirs 2h under the condition of 90 DEG C of constant temperature, leaves standstill after 24h, filters, and obtains NH
4vO
3precipitation.In sediment, add the appropriate pure water that is 9 by ammoniacal liquor regulator solution pH value, stir 2h, leave standstill cooling after, filtering-depositing, obtains the NH of one-level purifying
4vO
3sediment.Repeat to embathe NH with the Ammonia that pH value is 9
4vO
3sediment, is further purified NH
4vO
3precipitate, obtain the NH of one-level purifying
4vO
3sediment.By NH
4vO
3sediment obtains high-purity V at 450 DEG C of high-temperature calcination 2h
2o
5, according to vanadium: hydrazine=1: 0.3 mol ratio adds reducing agent hydrazine hydrate, the concentrated sulfuric acid is with hydrazine: sulfuric acid=1: 5 mol ratio adds, makes high-purity V
2o
5dissolving and reducing is VOSO completely
4solution.With graphite felt (area: 30 × 30cm
2) be the electrode material of electrolytic cell the moon/anode, domestic Nepem-211 cation-exchange membrane is separated the moon/anode, and assembling electrode area is 900cm
2single-stage module electrolytic cell.In anode fluid reservoir, put into 2.4 liters of tetravalence vanadium solutions, in negative electrode fluid reservoir, put into 4.8 liters of tetravalence vanadium solutions (tetravalence vanadium solution concentration is 1.54M), transport circulate electrolyte and flow through the moon/anode chamber of electrolytic cell with Western Hills magnetic force circulating pump, electrolysis under the condition of constant voltage 1.7V, cut-off current is 18A.Electrolysis 2 hours, in anode fluid reservoir, solution presents glassy yellow, and the tetravalence vanadium solution in negative electrode fluid reservoir is because of many one times of volume, has 50% tetravalence vanadium to be reduced to trivalent, and solution presents blue-green, has made the 3.5 valency vanadium solutions of 4.8 liters.Again when electrolysis, in anode chamber, add reducing agent taking vanadium/reducing agent mol ratio as 4 ratio, under strong acidic condition, can fast pentavalent vanadium be reduced to tetravalence vanadium, again as to electrode active material, with electrolytic preparation 3.5 valency vanadium solutions.If electrolyte volume equates with anode fluid reservoir volume in negative electrode fluid reservoir, negative electrode can make the trivalent vanadium electrolyte of 2.4 liters.Prepared tetravalence V electrolyte product, through chemical analysis, analysis result is as follows:
Embodiment 2
Get 6000 milliliters of NaVO containing vanadium 0.3M
3solution, regulator solution pH value is 9, adds aluminum sulfate (according to Si: Al=1: 1.4 mol ratio), leaves standstill 12h, filtering-depositing after adding thermal agitation 2h.In filtrate according to Ca: CO
3 2-=1: 1.2 mol ratios add sodium carbonate, and regulating the pH value of filtrate is 10, and Slow cooling after ebuillition of heated leaves standstill 12h, sedimentation and filtration.In reactor, add above-mentioned NaVO after preliminary impurity and purification
3solution, regulator solution acidity to pH value is 5, according to NH
4 +: V=2: 3 mol ratio adds ammonium chloride, stir after 1h, the pH=2 of regulator solution stirs 2h under the condition of 80 DEG C of constant temperature, leaves standstill after 12h, filters, and obtains NH
4vO
3precipitation.In sediment, add the appropriate pure water that is 10 by ammoniacal liquor regulator solution pH value, stir 2h, leave standstill cooling after, filtering-depositing, obtains the NH of one-level purifying
4vO
3sediment.By NH
4vO
3sediment obtains high-purity V at 550 DEG C of high-temperature calcination 2h
2o
5, according to vanadium: azanol=1: 0.25 mol ratio adds reducing agent hydrazine hydrate, the concentrated sulfuric acid is with hydrazine: azanol=1: 6 mol ratio adds, makes high-purity V
2o
5dissolving and reducing is VOSO completely
4solution.With porous carbon (area: 30 × 30cm
2) be the electrode material of electrolytic cell the moon/anode, the rich horse anion-exchange membrane of German import is separated the moon/anode, and assembling electrode area is 900cm
2single-stage module electrolytic cell.In sun/negative electrode fluid reservoir, respectively put into 5 liters of tetravalence vanadium solutions (tetravalence vanadium solution concentration is 1.6M), transport circulate electrolyte and flow through the moon/anode chamber of electrolytic cell with Western Hills magnetic force circulating pump, electrolysis under the condition of constant voltage 1.75V, electric current ends while being 15A, in anode fluid reservoir, solution presents glassy yellow, in negative electrode fluid reservoir, solution presents green, has made the trivalent vanadium solution of 5 liters.Again when electrolysis, in anode chamber, add reducing agent-azanol taking vanadium/reducing agent mol ratio as 4 ratio, under strong acidic condition, can fast pentavalent vanadium be reduced to tetravalence vanadium, again as to electrode active material, with electrolytic preparation 3 valency vanadium solutions.The trivalent vanadium solution of 5 liters mixes and makes 3.5 valency V electrolytes with equal-volume isoconcentration tetravalence vanadium solution.Prepared tetravalence V electrolyte product, through chemical analysis, analysis result is as follows:
。
Claims (8)
1. chemistry is combined a method for vanadium redox flow battery electrolyte processed with electrochemistry, it is characterized in that the method operating procedure is as follows:
(1) adopt vanadium slag leachate or containing the solid of soluble vanadium hydrochlorate or solution as raw material, adjust pH be alkalescence, adds cleaner, makes the impurity of the more high-leveled and difficult removal of content in vanadate solution form precipitation, filters removal;
(2) by vanadate solution adjust pH to 4～6 through preliminary removal of impurities of step (1) gained, add precipitation agent-ammonium sulfate, ammonium acetate, ammonium chloride or Ammonia, the mol ratio of the material of precipitation agent and vanadium is 1: 1～4: 1, carry out precipitation reaction, precipitation reaction temperature is 90～100 DEG C, reaction time is 0.5～3 hour, forms ammonium vanadate crystal settling, removes most of impurity;
(3) the ammonium vanadate sediment obtaining in step (2) is put into pure water, be heated with stirring to 80 DEG C, add ammoniacal liquor adjust pH is 8～10 simultaneously, fully stirs after 2 hours, static cooling, filters, and obtains the ammonium vanadate of one-level purifying;
(4) repeating step (3), can obtain the ammonium vanadate of multistage purifying;
(5) ammonium vanadate step (4) being obtained is calcined at 400～650 DEG C, and the time is 0.5～5 hour, obtains high-purity vanadic oxide;
(6) in sulfuric acid medium, step (2) high-purity vanadic oxide that obtains is reduced to tetravalence vanadium solution with soluble reducing agent, obtain the anode electrolyte for all-vanadium flow battery;
(7) the moon/anode that isopyknic tetravalence vanadium solution is placed in to electrolytic cell group carries out constant-potential electrolysis, and negative electrode obtains the trivalent vanadium electrolyte for all-vanadium flow battery negative pole; In the pentavalent vanadium solution that anode obtains, add soluble reducing agent, be converted into tetravalence vanadium solution; Isocyatic equal-volume trivalent vanadium solution and tetravalence vanadium solution are mixed, obtain all 3.5 valency V electrolytes of use of all-vanadium flow battery positive and negative electrode.
2. chemistry according to claim 1 is combined the method for vanadium redox flow battery electrolyte processed with electrochemistry, it is characterized in that described vanadium slag leachate or soluble vanadium hydrochlorate are the alkali metal salt of vanadic acid, metavanadic acid, pyrovanadic acid or their mixture, concentration is 0.5～50g/L; Cleaner is aluminium salt, magnesium salts and calcium salt, is 8～9 o'clock in pH value, removes silicate, chromate, phosphate radical anion in vanadate solution; PH is 10～12 o'clock, with the metal cation in cleaner-carbonate and sulfide removal vanadate solution.
3. chemistry according to claim 1 is combined the method for vanadium redox flow battery electrolyte processed with electrochemistry, it is characterized in that: the mol ratio of the material of cleaner aluminium salt and material liquid mesosilicic acid root is 1: 1～1.5: 1; In cleaner magnesium salts and material liquid, the mol ratio of the material of chromate is 1: 1～1.5: 1; In cleaner calcium salt and material liquid, the mol ratio of the material of phosphate radical is 0.9: 1～1.5: 1.In cleaner carbonate and material liquid, the mol ratio of the material of Ca or Mg ion is 0.9: 1～1.5: 1; In cleaner sulfide and material liquid, the mol ratio of the material of Ca or Cd ion is 0.8: 1～1.2: 1.
4. chemistry according to claim 1 is combined the method for vanadium redox flow battery electrolyte processed with electrochemistry, it is characterized in that soluble reducing agent is hydrazine, hydrazine sulfate, phenylhydrazine, phenylhydrazine sulfate, hydroxylammonium, HAS, diamine, hydrazine sulfate or their mixture.
5. chemistry according to claim 1 is combined the method for vanadium redox flow battery electrolyte processed with electrochemistry, and the molar ratio that it is characterized in that soluble reducing agent and vanadate or pentavalent barium oxide is the betatopic molal quantity of soluble reducing agent: the molal quantity of pentavalent vanadium is 1～8 times of the variable valence mumber inverse of soluble reducing agent.
6. chemistry according to claim 1 is combined the method for vanadium redox flow battery electrolyte processed with electrochemistry, it is characterized in that in step (7), electrolysis unit used comprises electrolytic cell group, negative electrode fluid reservoir, anode fluid reservoir, liquid transmission pipeline and pump, electrolytic cell group is 1 above electrolytic cell composition, electrolytic cell quantity is determined according to the daily output of electrolytic preparation V electrolyte, and negative electrode fluid reservoir is connected with the negative electrode of electrolytic cell group by liquid transmission pipeline through pump; Anode fluid reservoir is connected with the anode of electrolytic cell group by liquid transmission pipeline through pump; The collector plate of electrolytic cell is the composite plate of graphite cake or conducting polymer and the graphite of seepage-proof liquid densification, and negative electrode and anode material are porous carbon felt, porous graphite felt or porous carbon fiber; Barrier film between the moon/anode is cation-exchange membrane, anion-exchange membrane or anion/cation exchange composite membrane.
7. chemistry according to claim 1 is combined the method for vanadium redox flow battery electrolyte processed with electrochemistry, it is characterized in that electrolytic parameter is: constant-potential electrolysis mode, and the voltage between the moon/positive electrode is 1.7V; By detecting Current Control electrolysis terminal, terminal electric current is 10～80mA.
8. chemistry according to claim 1 is combined the method for vanadium redox flow battery electrolyte processed with electrochemistry, it is characterized in that: in V electrolyte, except v element and potassium, sodium, other metal impurities ion concentrations in electrolyte are all below 10ppm.
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| CN117374351A (en) * | 2023-12-07 | 2024-01-09 | 杭州德海艾科能源科技有限公司 | All-vanadium redox flow battery electrolyte and preparation method thereof |
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2013
- 2013-03-05 CN CN201310068952.2A patent/CN104037439A/en active Pending
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