CN103490086B - Preparation method of vanadium electrolyte - Google Patents
Preparation method of vanadium electrolyte Download PDFInfo
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- CN103490086B CN103490086B CN201310395458.7A CN201310395458A CN103490086B CN 103490086 B CN103490086 B CN 103490086B CN 201310395458 A CN201310395458 A CN 201310395458A CN 103490086 B CN103490086 B CN 103490086B
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- H01M8/00—Fuel cells; Manufacture thereof
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Abstract
The invention relates to a preparation method of a vanadium electrolyte, which comprises the following steps: dissolving vanadium pentoxide powder in a concentrated sulfuric acid for activation, adding into deionized water, dissolving and filtering to obtain a pentavalent vanadium ion solution; carrying out electrolysis by using the pentavalent vanadium ion solution as a negative electrode electrolyte solution and a sulfuric acid solution as a positive electrode electrolyte solution to obtain a vanadium ion electrolyte in which the mol ratio of trivalent vanadium to tetravalent vanadium is 1:1, wherein the molar weights of the sulfuric acid in the positive electrode electrolyte solution and the sulfuric acid in the negative electrode electrolyte solution are equal; and adding an additive into the vanadium ion electrolyte, and dissolving to obtain the vanadium electrolyte, wherein the additive comprises a phosphorous compound, and the mass percent of the compound in the vanadium electrolyte is 0.5-1.5%. The preparation method provided by the invention does not influence the service life of the vanadium battery and electrolyte on the premise of enhancing the concentration and stability of the electrolyte.
Description
Technical field
The invention belongs to field of batteries, particularly relate to a kind of preparation method of V electrolyte.
Background technology
Vanadium oxide reduction flow battery (abbreviation vanadium cell) is a kind of novel storage battery.Obtain because of features such as its cost are low, energy conversion efficiency is high and environmentally friendly and develop rapidly, progressively moving towards practical.In vanadium cell, adopt the solution of single vanadium metal ion as electrolyte, it comprises the different valence state ion (active material as vanadium cell) of sulfuric acid (as supporting electrolyte) and vanadium, and therefore other batteries of accumulate Performance Ratio of vanadium cell more depend on its electrolyte.In order to realize the high-energy-density of battery, requiring that electrolyte has high concentration, needing that again there is high stability simultaneously.
Compared with traditional battery, the energy storage capacity of vanadium cell and energy storage total value are determined by the concentration of often kind of vanadium ion in electrolyte and the volume of electrolyte.Therefore, electrolyte is a vital part of vanadium cell, and it is not only as conductor ion or energy-accumulating medium.But the vanadium ion dissolubility in the electrolytic solution of each valence state is limited, particularly when temperature rises to 40 DEG C, be limited by causing the specific energy density of V (V) in the electrolyte of vanadium cell.The concentration improving electrolyte solvent is considered to effective solution.In order to improve energy density and the capacity of vanadium cell, topmost method is exactly improve the concentration of vanadium ion in the electro-chemical activity of vanadium cell and electrolyte.Usually, the steady concentration of the vanadium in the electrolyte in vanadium cell can be about 1.8M, therefore in prior art, much research is all be devoted to improve vanadium ion concentration in electrolyte, and in electrolyte, add stabilizer is improve most economical, the most effective method of the one of vanadium cell performance.
But, existing a lot of additive contains the metal such as potassium, sodium, some additives contain nitrogen element, although do not see the performance change of electrolyte in a short time, but in the During Process of Long-term Operation of battery, can find that the additive containing these elements has very serious impact to the chemical property of vanadium cell and electrolyte and thermal stability, therefore the manufacturer of vanadium cell does not generally adopt the electrolyte containing additive.The electrolyte technology of additive is at present still in experimental stage.And electrolyte of vanadium redox battery real target will reach exactly, and concentration is high, purity is high, conductivity is high, the effect of good stability.
The chemical property (comprise the stability of Long-Time Service) of suitable element on electrolyte is selected not have to affect the even useful problem becoming electrolyte of vanadium redox battery research needs and solve, in the preparation process of electrolyte, how the range of choice of additive is determined or the range of choice that how to reduce additive is also the important topic that research improves concentration of electrolyte.Wish by adding special additive solution, electrolyte high temperature not to be separated out, low temperature is non-crystallizable, and in charge and discharge process, liquid level change is little, the equilibrium problem of positive and negative electrode electrolyte.
Summary of the invention
One or more in order in solving the problem, the invention provides a kind of preparation method of V electrolyte, wherein, comprise the following steps: vanadium pentoxide powder is placed in concentrated sulfuric acid dissolving and activates by (i), join dissolution filter in deionized water, obtain pentavalent vanadium ion solution; (ii) using described pentavalent vanadium ion solution as negative electrolyte solution, using sulfuric acid solution as catholyte solution, carry out electrolysis, the mol ratio obtaining trivalent vanadium and tetravalence vanadium is the vanadium ion electrolyte of 1:1, wherein, the sulfuric acid in catholyte is equal with the mole of the sulfuric acid in negative electrolyte solution; (iii) in the vanadium ion electrolyte obtained by described step (ii), additive is added, obtained described V electrolyte after dissolving; Described additive comprises phosphorous compound, and the mass percent concentration of described compound in described V electrolyte is 0.5% ~ 1.5%.
Wherein, the time carrying out activating in described step (ii) is 8 ~ 12 minutes.
Wherein, described vanadium pentoxide powder is purity is more than 99.9%.
Wherein, described V electrolyte is not containing other elements except C, H, O, P, V, S.
Wherein ,-OH group is contained in described additive.
Wherein, the organic component in described additive is not containing carbonyl.
Wherein, described phosphorous compound is any one or a few in phosphoric acid, hypophosphorous acid, phosphorous acid, pyrophosphoric acid, hypophosphoric acid, tripolyphosphate, excessively a phosphoric acid, peroxophosphoric acid.
Wherein, phosphorous compound is phosphoric acid.
The invention allows for the application of electrolyte in vanadium cell obtained by said method.
By the preparation method of V electrolyte provided by the invention under the raising concentration of electrolyte and the condition of stability, do not affect the life-span of vanadium cell and electrolyte.Compared with prior art, in the V electrolyte prepared by this method, the solubility of vanadium and utilance improve all greatly.
Accompanying drawing explanation
The not additivated V electrolyte cyclic voltammetry curve of Fig. 1.
The cyclic voltammetry curve of the V electrolyte that Fig. 2 is obtained by embodiment 1.
Embodiment
Below the additive used in the preparation method of V electrolyte according to the present invention and the method is described in detail.
According to one embodiment of present invention, a kind of preparation method of V electrolyte, said method comprising the steps of: vanadium pentoxide powder is placed in concentrated sulfuric acid dissolving and activates by (i), joins dissolution filter in deionized water, obtains pentavalent vanadium ion solution; (ii) using described pentavalent vanadium ion solution as negative electrolyte solution, using sulfuric acid solution as catholyte solution, carry out electrolysis, the mol ratio obtaining trivalent vanadium and tetravalence vanadium is the vanadium ion electrolyte of 1:1, wherein, the sulfuric acid in catholyte is equal with the mole of the sulfuric acid in negative electrolyte solution; (iii) in the vanadium ion electrolyte obtained by described step (ii), additive is added, obtained described V electrolyte after dissolving.Wherein, described additive comprises phosphorous compound, and the mass percent concentration of described compound in described V electrolyte is 0.5% ~ 1.5%.
Utilize according to method of the present invention, owing to the addition of the additive comprising phosphorus in V electrolyte, therefore, it is possible to form the supersaturated solution with higher vanadium steady concentration.Such as, in one embodiment of the invention, the steady concentration of vanadium can reach 5M.
Below the additive used in the preparation method to V electrolyte according to the present invention is illustrated in greater detail.
Due in process for extracting vanadium process, if the content of P is high in acid condition, then vanadium precipitation is more difficult, and pentavalent vanadium can not Precipitation.Generally will first except acid precipitation again after P, therefore P contributes to the solubility improving vanadium.In addition, present inventor finds that the existence of P can not affect the chemical property of electrolyte and vanadium cell.Therefore, in the preparation process of V electrolyte, add the additive containing P element compound, the solubility of vanadium ion in electrolyte can be improved in acid condition, and the chemical property of vanadium cell can not be affected.Compound phosphorous in the additive added can be inorganic phosphorous compound or organic phosphorus compound, is preferably any one or a few in phosphoric acid, hypophosphorous acid, phosphorous acid, pyrophosphoric acid, hypophosphoric acid, tripolyphosphate, excessively a phosphoric acid, peroxophosphoric acid.Present inventor finds, in the preparation method of V electrolyte provided by the invention, the mass percent concentration of phosphorous compound in V electrolyte comprised in additive should be 0.5% ~ 1.5%.Along with the increase of the content of additive, the charge/discharge capacity of electrolyte, coulombic efficiency, energy efficiency improve gradually, but the electrochemical utilization rate of vanadium in electrolyte can be made to reduce gradually after reaching certain scope, as: for the vanadium of 1.5mol, when the mass percent concentration of additive in V electrolyte is greater than 1.5%, the effect that the vanadium that the effect run in the battery is equivalent to 1.3mol runs in the battery.Be more preferably the mass percent concentration of phosphorous compound in V electrolyte comprised in additive and should be 0.8% ~ 1.4%, more preferably 1.0% ~ 1.3% is greater than this scope vanadium ion can be made to go hydration, reduce the stability of vanadium ion sulfuric acid solution on the contrary, the effect lower than this scope additive is bad.
In addition, inventor about impurity in the long-term research process of electrolyte and vanadium cell, find that most elements has adverse effect more or less to electrolyte or vanadium cell, therefore, in the preparation method of V electrolyte of the present invention, the additive added is preferably not containing other element beyond C, H, O, P, V; Namely, in the V electrolyte finally prepared by method provided by the invention, other element (i.e. impurity element) total content except C, H, O, P, V, S, at below 170ppm, when the content of impurity element is higher than 170ppm, will affect the electric property of vanadium cell.
Further, additive is also preferably in its organic component containing active group (-OH).Its reason is, the result of electrochemical impedance spectroscopy (EIS) shows that (-OH) improves electrolyte electrochemical activity, and the active group of increase is that electro transfer provides active place.Raman spectrum display VO
2 +ion and form a complex containing the additive of active group (-OH), this complex not only significantly improves V (V) electrolytical solubility, also for the redox reaction of V (IV)/V (V) provides more avtive spot.The number of active group is more simultaneously, and the electro-chemical activity of reaction is stronger.When additive has multiple (-OH), (-OH) arrangement is studied, find through nulcear magnetic resonance (NMR) (NMR) and cyclic voltammetry (CV) testing result, when multiple (-OH) group exists, sterically hindered less, the electro-chemical activity of electrolyte that obtains of additive is stronger thus.
Further, additive is also preferably its organic component not containing carbonyl (=O).Its reason is, when adding the additive of the organic component containing carbonyl, its carbonyl can reduce the electro-chemical activity of electrolyte.By doing additive containing two kinds of organic substances of carbonyl and hydroxyl, after cyclic voltammetry, find that the electro-chemical activity of the electrolyte of the additive containing carbonyl is weaker than the electro-chemical activity of not additivated electrolyte, and the electro-chemical activity of the electrolyte of the additive of hydroxyl is the strongest.
Below in conjunction with specific embodiment, the preparation method to V electrolyte of the present invention is described further, but the preparation method of V electrolyte of the present invention is not limited thereto.
embodiment 1
V
2o
5: high-grade pure (more than 99.9%)
H
2sO
4: analyze pure, d=1.84g/mL
H
3pO
4: analyze pure, d=1.834 × 10
3kg/m
3
I () takes high purity vanadic anhydride 320g, be dissolved in the concentrated sulfuric acid of 160mL, activates 10 minutes, and under the condition stirred, join in deionized water, be dissolved in water to 1L by slow for the pureed vanadium of activation, filtration obtains pentavalent vanadium solution.
(ii) measure the 160mL concentrated sulfuric acid, under the condition stirred, slowly join in deionized water, dissolve and obtain 1L sulfuric acid solution.The pentavalent vanadium solution obtained by above-mentioned steps (i) is joined the negative pole of electrolysis tank as electrolyte, the sulfuric acid solution prepared is joined the positive pole of electrolysis tank as electrolyte.The electric current of electrolysis is 20A, and the electricity of electrolysis is 506630C, electrolysis 7 hours.Through coulometry and oxidimetry determination terminal.The mol ratio obtaining trivalent vanadium and tetravalence vanadium is the vanadium ion electrolyte of 1:1.
(iii) measure and analyze pure phosphoric acid 8mL as additive, be added with in the vanadium ion electrolyte that above-mentioned steps (iii) obtains.Wherein, phosphoric acid mass fraction is in the electrolytic solution about 1%.
Wherein, in order to avoid the impact of other impurity elements, the purity of vanadic oxide is more than 99.9%.In addition, because vanadic oxide exists in the solution in colloidal form, be difficult to be dissociated into pentavalent vanadium ion, adopt concentrated sulfuric acid activation, make vanadium almost all be ionized into pentavalent vanadium ion, be conducive to follow-up electrolytic process, it also avoid the waste of vanadium resource.In addition, the electric current of electrolysis in step (ii), electrolysis time and electricity etc. all can be selected according to actual needs flexibly.
Wherein, the pentavalent vanadium solution preparation in step (i) is preferably V
2o
5: H
2sO
4: H
2o=182:12:835 (mass ratio g:g:g), first measure 165mL and analyze pure concentrated sulfuric acid dissolution in 70mL water, obtain sulfuric acid solution, 182g vanadic oxide is joined in sulfuric acid solution and dissolves, heat 2 minutes at 150 DEG C, utilize waste heat to activate 8 minutes, period reduces moisture evaporation as far as possible, add deionized water 770mL again after cooling, filter and obtain pentavalent vanadium solution.
embodiment 2 ~ 4
Step (i) is identical with above-described embodiment 1 with (ii), adds additive as shown in table 1 respectively as embodiment 2 ~ 4 in step (iii)
comparative example 1 ~ 2
Step (i) is identical with above-described embodiment 1 with (ii), adds additive as shown in table 1 respectively as embodiment 1 ~ 2 in step (iii)
The different additive that table 1 adds and content
By the V electrolyte prepared by said method compared with the V electrolyte concentration 1.8mol/L conventionally prepared, reach 3.5mol/L by the concentration of the electrolyte of above-mentioned preparation.Further, left standstill by the V electrolyte part of the embodiment of the present invention 1 ~ 4 gained and partly run nearly one month in the battery without Precipitation, stability is higher than V electrolyte of the prior art.But, in comparative example 1, no matter the V electrolyte of gained is leave standstill or have in negative pole after running one month in the battery to precipitate generation on a small quantity, its stability is lower than the stability of the V electrolyte not containing other elements (as Na), and the electrolyte in comparative example 2 runs in negative pole in the battery separates out more precipitations.
Below, under different scanning speed, do cyclic voltammetry respectively to the V electrolyte of embodiment 1 and the V electrolyte that do not add any additive, sweep limits [-1.0V, 1.5V] is swept speed and is respectively 3mVs
-1, 5m Vs
-1, 10mVs
-1, gained cyclic voltammetry curve is shown in Fig. 1 and Fig. 2.From the position judgment at peak, A is the oxidation peak of V (IV) to V (V), and B is the reduction peak corresponding with A; C is the oxidation peak of V (II) to V (III), and D is the reduction peak corresponding with C.
Cyclic voltammetry uses electrochemical workstation (Tong Zhong Co., Ltd of Switzerland ten thousand, China) to realize between 0V and 1.6V under the sweep speed of 5.0mv.The electrode unit of three kinds of electrodes is respectively using platinum electrode as auxiliary electrode, and saturated calomel electrode is as reference electrode, and area is 1.0cm
2graphite electrode as work electrode.Graphite electrode 600 (P1200) gravel carborundum polishing paper disk, then cleans with deionized water.In order to avoid different ions is polluted at electrode surface intersections, graphite electrode should polishing and cleaning after each test.
Carry out discharge and recharge test to embodiment 1 ~ 4 and comparative example 1 ~ 2, the discharge and recharge of vanadium cell test carries out in a little monocell, and its uses perfluorinated sulfonic acid ion exchange membrane (E.I.Du Pont Company, China) as barrier film.Two pieces of areas are 9.0cm
2through the graphite felt of modification anti-corrosion treatment as the positive pole of vanadium cell and negative pole, using isocyatic trivalent and tetravalent vanadium ion solution as electrolyte, the TV concentration of electrolyte is 2.5mol/L.Discharge and recharge test realizes by using CT2001D-10A/20V (Wuhan Lan electricity Electronics Co., Ltd., China).Battery setting voltage is between 0.8-1.7V, and current density is 60mA/cm
2condition under to carry out discharge and recharge.Experimental comparison results is in table 2.
The electrolyte of table 2 different additive runs the average result of 20 circulations in the battery
| Execution mode | Current efficiency | Energy efficiency | The utilance of vanadium | Concentration of electrolyte |
| Blank | 90％ | 80％ | 94％ | 1.8mol/L |
| Embodiment 1 | 95％ | 83％ | 98％ | 2.5mol/L |
| Embodiment 2 | 90％ | 79％ | 94％ | 2.5mol/L |
| Embodiment 3 | 94％ | 81％ | 95％ | 2.5mol/L |
| Embodiment 4 | 97％ | 86％ | 98％ | 2.5mol/L |
| Comparative example 1 | 85％ | 67％ | 80％ | 2.5mol/L |
| Comparative example 2 | 78％ | 65％ | 60％ | 2.5mol/L |
Known and the blank of table 2, embodiment 1 ~ 4 can meet or exceed blank operation result under concentration is 2.5mol/L, and the utilance of vanadium does not reduce, and both positive and negative polarity does not have Precipitation simultaneously; Implement 2 ~ 4 also can find, phosphoric acid is 3-OH, and metaphosphoric acid is 1-OH, and phosphorous acid is that the more charge-discharge performances to battery of the number of 2-OH ,-OH are better; Comparative example 1,2 charge-discharge performance when starting is fine, but after the several circulation of operation, negative pole starts to occur crystallization, causes the rate of decay to be accelerated, and the charge-discharge performance in later stage declines, overall discharge and recharge poor effect, especially comparative example 2.Sodium can affect battery performance as the additive of electrolyte, especially the performance of negative pole, and by finding the related experiment of barrier film, sodium can move on barrier film, some sodium can on barrier film crystallization, make barrier film hardening, affect the selectivity of barrier film.
Carry out electrochemical analysis to embodiment 1 and blank, electrochemical impedance spectrometry adopts AUT302N-FRA2.V electrochemical workstation (Switzerland ten thousand leads to, China).Sinusoidal voltage is 5mV, and frequency range is between 0.001 hertz to 100 kilo hertzs.Raman spectrum use for laboratory Labram-010 spectrophotometric analysis is not containing the total class of vanadium ion in the electrolyte of vanadium redox battery of additive.Additive is studied by cyclic voltammetry (CV), discharge and recharge technology, electrochemical impedance spectroscopy (EIS), raman study the impact of electrolyte.Result shows, adopts the redox vanadium electrolyte meter of the electrolyte of the additive of phosphoric acid to reveal best chemical property (energy efficiency of 85.8%).
The result of electrochemical impedance spectroscopy (EIS) shows, phosphoric acid improves electrolyte electrochemical activity.Find that phosphoric acid additive makes to shift between vanadium ion and electronics more feasible in electron transfer reaction, be more conducive to the Charger transfer of redox reaction, the conductivity of electrolyte is not almost affected.Again because increase active group (-OH) for electro transfer provides active place, so phosphoric acid has better electro-chemical activity than other phosphorus-containing compounds.Raman spectrum display VO
2 +ion and phosphoric acid participate in formation complex, and this complex not only significantly improves V (V) electrolytical solubility, also for the redox reaction of V (IV)/V (V) provides more avtive spot.
By the preparation method of V electrolyte provided by the invention, have the following advantages:
1., under the raising concentration of electrolyte and the condition of stability, do not add any harmful impurity, do not affect the life-span of vanadium cell and electrolyte.
2. because vanadic oxide exists in the solution in colloidal form, be difficult to be dissociated into pentavalent vanadium ion, adopt concentrated sulfuric acid activation, make vanadium almost all be ionized into pentavalent vanadium ion, be conducive to follow-up electrolytic process, it also avoid the waste of vanadium resource.
3., by adopting purity to be the vanadic oxide of more than 99.9%, the analytically pure concentrated sulfuric acid and deionized water, control the content of impurity element in V electrolyte; Owing to not introducing any impurity in preparation process, and in V electrolyte, do not add additive and the impurity element of any other elements except C, H, O, P, V, increase the solubility of electrolyte while therefore not affecting the performance of vanadium cell and improve the utilance of vanadium in electrolyte.
Claims (8)
1. a preparation method for V electrolyte, is characterized in that, comprises the following steps:
I vanadium pentoxide powder is placed in the dissolving of the analytically pure concentrated sulfuric acid and activates by (), join dissolution filter in deionized water, obtain pentavalent vanadium ion solution;
(ii) using described pentavalent vanadium ion solution as negative electrolyte solution, using sulfuric acid solution as catholyte solution, carry out electrolysis, the mol ratio obtaining trivalent vanadium and tetravalence vanadium is the vanadium ion electrolyte of 1:1, wherein, the sulfuric acid in catholyte is equal with the mole of the sulfuric acid in negative electrolyte solution;
(iii) in the vanadium ion electrolyte obtained by described step (ii), add additive, obtained described V electrolyte after dissolving, wherein, described V electrolyte does not contain other elements except C, H, O, P, V, S,
Wherein, described additive comprises phosphorous compound, and the mass percent concentration of described phosphorous compound in described V electrolyte is 0.5% ~ 1.5%.
2. the preparation method of V electrolyte according to claim 1, it is characterized in that, the time carrying out in described step (i) activating is 8 ~ 12 minutes.
3. the preparation method of V electrolyte according to claim 1, it is characterized in that, the purity of described vanadium pentoxide powder is more than 99.9%.
4. the preparation method of V electrolyte according to claim 1, is characterized in that, containing-OH group in described additive.
5. the preparation method of V electrolyte according to claim 1, is characterized in that, the organic component in described additive is not containing carbonyl.
6. the preparation method of V electrolyte according to claim 1, is characterized in that, described phosphorous compound is phosphoric acid, hypophosphorous acid, phosphorous acid, pyrophosphoric acid, hypophosphoric acid, tripolyphosphate, cross in a phosphoric acid, peroxophosphoric acid any one or a few.
7. the preparation method of V electrolyte according to claim 6, it is characterized in that, phosphorous compound is phosphoric acid.
8. by the application of electrolyte in vanadium cell prepared by the method described in claim 1 to 7 any one.
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| CN104577173B (en) * | 2015-01-07 | 2017-05-31 | 攀钢集团研究院有限公司 | The method that electrolyte for vanadium cell is directly prepared using vanadic anhydride |
| CN106299432A (en) * | 2015-05-26 | 2017-01-04 | 中国科学院金属研究所 | Mineral acid is as improving V electrolyte concentration and the application of stability additive |
| CN109768309A (en) * | 2017-11-09 | 2019-05-17 | 中国科学院大连化学物理研究所 | A kind of application of electrolyte liquid in all-vanadium flow battery |
| CN108199068B (en) * | 2018-01-09 | 2020-05-05 | 中国工程物理研究院电子工程研究所 | Low-temperature all-vanadium redox flow battery electrolyte and preparation method thereof |
| CN114142075B (en) * | 2021-11-30 | 2023-10-27 | 成都先进金属材料产业技术研究院股份有限公司 | Preparation method of vanadium redox flow battery electrolyte |
| CN114335645A (en) * | 2021-12-23 | 2022-04-12 | 大连博融新材料有限公司 | Chlorine-vanadium-containing electrolytic liquid crystal, preparation method and application thereof |
| CN117558956B (en) * | 2023-12-29 | 2024-04-05 | 山西国润储能科技有限公司 | Preparation method of high-stability vanadium electrolyte |
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| US20040241552A1 (en) * | 2001-05-18 | 2004-12-02 | Maria Skyllas-Kazacos | Vanadium redox battery electrolyte |
| CN101692500A (en) * | 2009-10-23 | 2010-04-07 | 攀钢集团研究院有限公司 | Method for preparing all-vanadium ionic liquid flow battery electrolyte and prepared electrolyte |
| CN102110836A (en) * | 2011-01-26 | 2011-06-29 | 上海林洋储能科技有限公司 | High-reliability vanadium ion electrolyte |
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