CN101174705A - Method for preparing all vanadium ion redox flow battery electrolyte - Google Patents
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Abstract
The present invention relates to the field of battery manufacturing and energy storage, in particular to the electrolytic preparation method of high-concentration full-vanadium-ion redox flow battery (vanadium battery) electrolyte solution. With V2O5 and V2O3 as the main raw materials and the addition of an organic-inorganic compound additive in a proper proportion, the method adopts an electrolytic method and low-cost raw materials so as to prepare the vanadium battery electrolytic solution with 5-6mol/L concentration. The present invention has the advantages of simple process, easy operation, low-cost raw materials, ability to obtain the vanadium battery electrolytic solution with high-concentration and good stability, good electrochemical reversibility of the electrolytic solution, conductivity close to the conventional 2mol/L electrolyte, and ability to achieve the battery charge and discharge.
Description
Technical field
The present invention relates to battery manufacturing and energy field of storage, be specially the electrolytic preparation method of all vanadium ion redox flow battery electrolyte of a kind of high concentration, good stability.
Background technology
All vanadium ion redox flow battery is called for short vanadium cell, is a kind of new green environment protection battery.As a kind of flow battery, its energy stores with the form of both positive and negative polarity electrolyte, and the both positive and negative polarity reaction is respectively:
Anodal reaction: VO
2 ++ 2H
++ e
-→ VO
2++ H
2O E
0=1.00V
Negative reaction: V
3++ e
-→ V
2+E
0-0.26V
Each is driven both positive and negative polarity electrolyte by a pump, and reduction and oxidation reaction take place respectively on the electrode of amberplex both sides, finishes discharging and recharging.Therefore, electrolyte solution is the core of flow battery, and its concentration is the greatest factor of decision energy density.It is a multivalence attitude system, is realizing the storage and the release of energy.Owing to occur the precipitation of vanadium species phenomenon such as condense in actual the use, make the present working concentration of electrolyte of vanadium redox battery about 2mol/L, energy density lower (25Wh/kg).Therefore both needed the high-energy-density of the electrolyte solution of high concentration in reality, and required it that high stability is arranged again with the realization battery.This is the key technical problem that vanadium cell enters the urgent need solution in practicability stage.
The preparation method of electrolyte that adopts mainly contains at present: 1. with V
2O
5Mix with a certain amount of concentrated sulfuric acid, obtain VOSO after the dissolving
4Solution is assembled into battery with this solution then and charges, and obtains V (vanadium) solution after finishing.With the concentrated sulfuric acid with distilled water by 1: 1 dilution proportion, add V
2O
3, progressively add V again
2O
5, cooled and filtered, that obtain blueness is VOSO
4Acid solution carries out discharging and recharging of battery then.3. with VOSO
4Directly be dissolved in (1-9mol/L) in the sulfuric acid, carry out discharging and recharging of battery then.4. with NH
4VO
3Be dissolved in the certain density concentrated sulfuric acid, obtain VO
2+, V
3+, NH
4 +, SO
4 2-The system of coexistence, this system can directly be carried out discharging and recharging of battery, obtains the required electrolyte of both positive and negative polarity.
Have research to improve the stability of electrolyte and the solubility of vanadium ion, but concentration is not fairly obvious with the raising of stability by adding glycerine and sodium sulphate (2%).
Said method all fails the concentration of electrolyte of vanadium redox battery and stability are significantly improved.
Summary of the invention
The present invention is directed to above problem, the electrolytic preparation method of all vanadium ion redox flow battery (vanadium cell) electrolyte of a kind of high concentration, good stability is proposed, the concentration of electrolyte of vanadium redox battery is brought up to 5-6mol/L, and can stablize deposited phenomenon did not take place more than 6 months, and finished the preliminary test that discharges and recharges.
Technical scheme of the present invention is:
With vanadic oxide (V
2O
5) and vanadium trioxide (V
2O
3) be raw material, add the organic-inorganic composite additive of proper proportion, by in electrolytic cell, carrying out the method for electrolysis, the electrolyte of vanadium redox battery of preparation high concentration, good stability.The preparation method is as follows:
1, electrolytic method is realized by electrolytic cell, and electrolytic cell is made of positive and negative half pond, and the centre separates with cation exchange membrane, and just the electrode that inserts in half pond links to each other with the positive pole of DC power supply, and the electrode that inserts in negative half pond links to each other with the negative pole of DC power supply.Positive and negative electrode adopts high purity graphite electrode or dimensionally stable electrode (DSA electrode, Dimensionally Stable Anode), and electrolysis mode adopts constant-current electrolysis, and current density is: 20-500mA/cm
2, electrolysis time is 5～20 hours.
2, preparation organic-inorganic composite additive, wherein organic additive comprise following one or more: (1) ethylenediamine, diethylenetriamine, triethylene tetramine, aliphat amine and aromatic polyamine compounds such as aniline, and pyridine, imidazoles, quinoline, 1, nitrogen heterocyclic ring compounds such as the luxuriant and rich with fragrance network quinoline of 10-; (2) EGTA, EDTP, DTPA, EDTA etc. contain aminopolycanboxylic acid's class intercalating agent compound of amino oxalic acid group; (3) sulfur heterocyclic ring compounds such as thiazole, 2-(2,4 one two basic phenyl sulfo-) benzene a pair of horses going side by side thiazole; (4) oxygen heterocycle such as furans, pyrans compounds.Inorganic additive comprise following one or more: the nitrate of alkali metal, alkaline-earth metal, sulfate, disulfate, bicarbonate, chloride.Wherein, DTPA is a diethylene triamine pentacetic acid (DTPA), and EDTP is the ethylenediamine tetraacetic n Propanoic acid, and EDTA is an ethylenediamine tetra-acetic acid, and EGTA is ethylene glycol bis (alpha-amido ethyl) ether tetraacethyl.
Among the present invention, organic and molar ratio inorganic additive is (0: 1)～(8: 1), and the concentration of compound additive in electrolyte is 0.1mol/L～2 mol/L.Wherein, the preferred proportion of organic additive and inorganic additive is (0.5: 1)～(4: 1) in the compound additive, and the preferred concentration of compound additive in electrolyte is 0.2mol/L～lmol/L.
3, during electrolysis, be sulfuric acid solution, the V of 2～5mol/L for concentration in negative half pond
2O
5And V
2O
3Powder, wherein V
2O
3And V
2O
5Mol ratio be (0: 1)～(1: 1), preferable mol ratio is (0.2: 1)-(0.8: 1), sulfuric acid and V
2O
5Mol ratio be (1: 1)～(2: 1).Just putting in half pond and the sulfuric acid solution of negative half pond equivalent with concentration.Stir down, add compound additive to negative half pond, surfactant (as: the cetyl benzene sulfonic acid sodium salt that adds electrolyte weight 1-5% simultaneously, dodecyl sodium sulfate, cetyl front three ammonium chloride, cetyl front three ammonium bromide, sodium hexadecyl sulfate or OPl0 etc.), carry out electrolysis under the DC power supply.After electrolysis finishes, will bear half pond electrolysis gained solution and filter, obtain required electrolyte.The concentration of vanadium ion in electrolyte is 5-6mol/L.Wherein, sulfuric acid provides H as supporting electrolyte
+, surfactant plays the hydrotropy effect.
Among the present invention, the interpolation of compound additive promptly can constantly be added in electrolyte in electrolytic process in different ways; Can before electrolysis additive and sulfuric acid be made into mixed solution again, the mixture of vanadic oxide or vanadic oxide and vanadium trioxide be dissolved in the electrolysis of carrying out in the mixed solution again, the obtained effect of these two kinds of addition manners is identical.
Among the present invention, add surfactant in electrolysis of solutions process, surfactant adopts anion surfactant, cationic surfactant, non-ionic surface active agent, and its effect is the generation that precipitates in the inhibition electrolytic process.Wherein, anion surfactant can be the cetyl benzene sulfonic acid sodium salt, in dodecyl sodium sulfate or the sodium hexadecyl sulfate one or more, cationic surfactant can be one or more of hexadecyltrimethylammonium chloride, softex kw or DTAB, and non-ionic surface active agent can be one or more of polyethylene glycol oxide uncle octylphenol ether, polyoxyethylene nonylphenol ether or NPE (OPl0).
Advantage of the present invention:
1, the present invention is a raw material with vanadic oxide and vanadium trioxide, adopts the method for the organic-inorganic composite additive that adds proper proportion, makes the required electrolyte of vanadium cell by electrolysis.Process of the present invention is simple, processing ease, and raw material is vanadic oxide and vanadium trioxide, and cost is low, can obtain the electrolyte of vanadium redox battery of high concentration, good stability, and wherein vanadium ion concentration can reach 5-6mol/L.The effect of compound additive is to suppress in the electrolytic process vanadium plasma and precipitation of the same race and that the association xenogenesis ion causes and separates out, and inorganic additive is also as supporting electrolyte simultaneously.The electrochemical reversibility of electrolyte of the present invention is good, and conductivity approaches conventional 2mol/L electrolyte, discharges and recharges test and demonstrates this solution and have higher discharge voltage, and the potentiality that improve vanadium cell specific energy and specific power are arranged.
2, organic-inorganic composite additive of the present invention, its main component is environmentally friendly material, can not produce adverse effect to environment, meets the feature of the environmental protection of vanadium cell.And consumption is low, can not affect greatly the cost of vanadium cell.
Description of drawings
Fig. 1 stores the photomacrograph of 6 months front and back for 5mol/L electrolyte of the present invention.
Fig. 2 is 5mol/L electrolyte of the present invention and conventional 2mol/LVOSO
4+ 2mol/L H
2OSO
4Cyclic voltammetry curve contrast.
Fig. 3 is an electrolyser construction schematic diagram of the present invention.Among the figure, 1 DC power supply, 2 negative poles, 3 negative half ponds, 4 blenders, 5 positive poles, 6 half ponds just, 7 barrier films.
Embodiment
As shown in Figure 3, electrolytic cell is made up of positive and negative two half-cells, and two half-cells are separated by barrier film 7 (cation-exchange membrane).Just the electrode that inserts in half pond 6 links to each other with the positive pole 5 of DC power supply 1, and the electrode that inserts in negative half pond 3 links to each other with the negative pole 2 of DC power supply 1, is provided with blender 4 in negative half pond 3.
The sulfuric acid solution 90ml and 60 that adds 2mol/L in negative half pond of electrolytic cell restrains vanadic oxides, is just putting into the sulfuric acid solution of 2mol/L in half pond, makes the liquid level in the two halves pond equal, and just the DSA electrode is adopted in half pond, and graphite electrode is adopted in negative half pond, with 20mA/cm
2Current density carry out electrolysis, electrolysis time is 20h.Constantly add additive in negative half pond of electrolytic cell in electrolytic process, the composition of the additive of interpolation and consumption are: 0.005mol ethylenediamine, 0.005mol pyridine, 0.005mol thiazole, 0.006mol KNO
3, 0.006mol NaNO
3, 0.004mol EDTA.Use GB GB 8639.1-88 that the negative half pond electrolyte after filtering is carried out concentration determination, show that vanadium ion concentration is 5.1mol/L.
With graphite is positive and negative pole material, and both positive and negative polarity solution is that the prepared vanadium ion concentration that contains of electrolysis is 5.1mol/L electrolyte, and the density of charging current is 11.5mA/cm
2, discharge current density is 4mA/cm
2, getting incipient discharge voltage is 1.96V, and average discharge volt is 1.24V, and voltage efficiency is 60%, and energy efficiency is 75%.
The sulfuric acid solution 90ml and 60 gram vanadic oxides and the 50 gram vanadium trioxides that in negative half pond of electrolytic cell, add 3mol/L, just putting into the sulfuric acid solution of 3mol/L in half pond, making the liquid level in the two halves pond equal, just the DSA electrode is adopted in half pond, graphite electrode is adopted in negative half pond, with 100mA/cm
2Current density carry out electrolysis, electrolysis time is 8h.Constantly add additive in negative half pond of electrolysis in electrolytic process, the composition of the additive of interpolation and consumption are: 0.004mol ethylenediamine, 0.004mol pyridine, 0.004mol thiazole, 0.01mol KNO
3, 0.01mol NaNO
3, 0.01mol EDTA.Use GB GB 8639.1-88 that the negative half pond electrolyte after filtering is carried out concentration determination, show that vanadium ion concentration is 5.2mol/L.
With graphite is positive and negative pole material, and to be that electrolysis is prepared contain the electrolyte that vanadium ion concentration is 5.2mol/L to both positive and negative polarity solution, and the density of charging current is 20mA/cm
2, discharge current density is 5mA/cm
2, getting incipient discharge voltage is 1.85V, and average discharge volt is 1.25V, and voltage efficiency is 65%, and energy efficiency is 80%.
The sulfuric acid solution 90ml and 50 gram vanadic oxides and the 30 gram vanadium trioxides that in negative half pond of electrolytic cell, add 4mol/L, just putting into the sulfuric acid solution of 4mol/L in half pond, making the liquid level in the two halves pond equal, just the DSA electrode is adopted in half pond, graphite electrode is adopted in negative half pond, with 300mA/cm
2Current density carry out electrolysis, electrolysis time is 4h.Constantly add additive in negative half pond of electrolysis in electrolytic process, the composition of the additive of interpolation and consumption are: 0.004mol ethylenediamine, 0.004mol pyridine, 0.004mol thiazole, 0.02mol KNO
3, 0.02mol KHSO
4, 0.01mol LiCl
2, 0.005mol EGTA.When 1h is carried out in electrolysis, add 3 gram cetyl benzene sulfonic acid sodium salts to negative half pond.With GB GB 8639.1-88 the negative half pond electrolyte after filtering is carried out concentration determination, show that vanadium ion concentration is 5.2mol/L.
With graphite is positive and negative pole material, and to be that electrolysis is prepared contain the electrolyte that vanadium ion concentration is 5.2mol/L to both positive and negative polarity solution, and the density of charging current is 200mA/cm
2, discharge current density is 30mA/cm
2, getting incipient discharge voltage is 1.95V, and average discharge volt is 1.30V, and voltage efficiency is 68%, and energy efficiency is 81%.
The sulfuric acid solution 90ml and 50 gram vanadic oxides and the 30 gram vanadium trioxides that in negative half pond of electrolytic cell, add 5mol/L, just putting into the sulfuric acid solution of 5mol/L in half pond, making the liquid level in the two halves pond equal, just the DSA electrode is adopted in half pond, graphite electrode is adopted in negative half pond, with 500mA/cm
2Current density carry out electrolysis, electrolysis time is 2h.Constantly add additive in negative half pond of electrolytic cell in electrolytic process, the composition of the additive of interpolation and consumption are: 0.002mol diethylenetriamine, 0.002mol imidazoles, 0.002 mol thiazole, 0.02molCaCl
2, 0.04mol KHSO
4, 0.02mol KNO
3, 0.002 mol DTPA.When 30min is carried out in electrolysis, add 3 gram hexadecyltrimethylammonium chlorides to negative half pond.With GB GB 8639.1-88 the negative half pond electrolyte after filtering is carried out concentration determination, show that vanadium ion concentration is 5.2mol/L.
With graphite is positive and negative pole material, and to be that electrolysis is prepared contain the electrolyte that vanadium ion concentration is 5.2mol/L to both positive and negative polarity solution, and the density of charging current is 200mA/cm
2, discharge current density is 30mA/cm
2, getting incipient discharge voltage is 1.95V, and average discharge volt is 1.30V, and voltage efficiency is 68%, and energy efficiency is 81%.
In the 500ml beaker, add about 100ml water, the 60ml concentrated sulfuric acid, add additive again: 0.001mol triethylene tetramine, 0.001mol furans, 0.05mol NaHSO
4, 0.01mol K
2SO
4, 0.03mol KHSO
4, 0.001mol EDTP is cooled to room temperature, moves in the 250ml volumetric flask, adds water to scale, and sulfuric acid solution concentration is 5mol/L, and the concentration of compound additive is 0.37mol/L.
Add this mixed liquor 100ml and 50 gram vanadic oxides and 40 gram vanadium trioxides in negative half pond of electrolytic cell, just put into this mixed solution in half pond, make the liquid level in the two halves pond equal, just the DSA electrode is adopted in half pond, and graphite electrode is adopted in negative half pond, with 400mA/cm
2Current density carry out electrolysis, electrolysis time is 3h.With GB GB 8639.1-88 the negative half pond electrolyte after filtering is carried out concentration determination, show that vanadium ion concentration is 5.5mol/L.
With graphite is positive and negative pole material, and to be that electrolysis is prepared contain the electrolyte that vanadium ion concentration is 5.5mol/L to both positive and negative polarity solution, and the density of charging current is 100mA/cm
2, discharge current density is 10mA/cm
2, getting incipient discharge voltage is 1.98V, and average discharge volt is 1.32V, and voltage efficiency is 65.5%, and energy efficiency is 81%.
In the 500ml beaker, add about 100ml water, the 55ml concentrated sulfuric acid, add additive again: 0.002mol triethylene tetramine, 0.002mol quinoline, 0.002mol 2-(2,4 one two basic phenyl sulfo-) the parallel thiazole of benzene, 0.02molKNO
3, 0.04mol KHSO
4, 0.02mol MgCl
2, 0.002mol EGTA is cooled to room temperature, moves in the 250ml volumetric flask, adds water to scale, and sulfuric acid solution concentration is 4mol/L, and the concentration of compound additive is 0.35mol/L.
Add this mixed liquor 100ml and 50 gram vanadic oxides and 20 gram vanadium trioxides in negative half pond of electrolytic cell, just put into this mixed solution in half pond, make the liquid level in the two halves pond equal, just the DSA electrode is adopted in half pond, and graphite electrode is adopted in negative half pond, with 300mA/cm
2Current density carry out electrolysis, electrolysis time is 5h.With GB GB 8639.1-88 the negative half pond electrolyte after filtering is carried out concentration determination, show that vanadium ion concentration is 5.2mol/L.
With graphite is positive and negative pole material, and to be that electrolysis is prepared contain the electrolyte that vanadium ion concentration is 5.2mol/L to both positive and negative polarity solution, and the density of charging current is 100mA/cm
2, discharge current density is 10mA/cm
2, getting incipient discharge voltage is 1.90V, and average discharge volt is 1.28V, and voltage efficiency is 66%, and energy efficiency is 78%.
Embodiment 7
Add about 100ml water, the 45ml concentrated sulfuric acid in the 500ml beaker, add additive again: 0.001mol aniline, 0.001mol 1, the luxuriant and rich with fragrance network quinoline of 10-, 0.001mol furans, 0.01mol CaCl
2, 0.003mol Na
2SO
4, 0.04mol KHSO
4, 0.001molEDTA is cooled to room temperature, moves in the 250ml volumetric flask, adds water to scale, and sulfuric acid solution concentration is 3.4mol/L, and the concentration of compound additive is 0.23mol/L.
Add this mixed liquor 100ml and 70 gram vanadic oxides and 30 gram vanadium trioxides in negative half pond of electrolytic cell, just put into this mixed solution in half pond, make the liquid level in the two halves pond equal, just the DSA electrode is adopted in half pond, and graphite electrode is adopted in negative half pond, with 500mA/cm
2Current density carry out electrolysis, electrolysis time is 2h.When 1h is carried out in electrolysis, add 3 gram polyethylene glycol oxide uncle octylphenol ethers to negative half pond.With GB GB 8639.1-88 the negative half pond electrolyte after filtering is carried out concentration determination, show that vanadium ion concentration is 5.2mol/L.
With graphite is positive and negative pole material, and to be that electrolysis is prepared contain the electrolyte that vanadium ion concentration is 5.2mol/L to both positive and negative polarity solution, and the density of charging current is 100mA/cm
2, discharge current density is 10mA/cm
2, getting incipient discharge voltage is 1.90V, and average discharge volt is 1.28V, and voltage efficiency is 66%, and energy efficiency is 78%.
Embodiment 8
In the 500ml beaker, add about 100ml water, the 35ml concentrated sulfuric acid, add additive again: 0.002mol triethylene tetramine, 0.002mol quinoline, 0.002mol thiazole, 0.02mol KNO
3, 0.05mol KHSO
4, 0.02mol CaCl
2, 0.002mol EGTA is cooled to room temperature, moves in the 250ml volumetric flask, adds water to scale, and sulfuric acid solution concentration is 2.6mol/L, and the concentration of compound additive is 0.4mol/L.
Add this mixed liquor 100ml and 80 gram vanadic oxides and 30 gram vanadium trioxides in negative half pond of electrolytic cell, just put into this mixed solution in half pond, make the liquid level in the two halves pond equal, just the DSA electrode is adopted in half pond, and graphite electrode is adopted in negative half pond, with 300mA/cm
2Current density carry out electrolysis, electrolysis time is 8h.When 4h is carried out in electrolysis, add 3 gram dodecyl sodium sulfates, softex kw and polyoxyethylene nonylphenol ether to negative half pond and get mixture, three's weight ratio is 1: 1: 1.With GB GB 8639.1-88 the negative half pond electrolyte after filtering is carried out concentration determination, show that vanadium ion concentration is 5.5mol/L.
With graphite is positive and negative pole material, and to be that electrolysis is prepared contain the electrolyte that vanadium ion concentration is 5.5mol/L to both positive and negative polarity solution, and the density of charging current is 100mA/cm
2, discharge current density is 10mA/cm
2, getting incipient discharge voltage is 1.90V, and average discharge volt is 1.28V, and voltage efficiency is 66%, and energy efficiency is 78%.
The electrolyte of vanadium redox battery concentration that the present invention obtains can be brought up to 5-6mol/L, leaves standstill not precipitate (see Fig. 1, A is for before storing, and B is for after storing 6 months), its conductivity (15.41mS/cm, 30 ℃) and conventional 2mol/LVOSO in 6 months
4The conductivity of solution (19.28mS/cm, 30 ℃) differs very little, illustrates that it is approaching with species and conventional soln that ionic species exists.As shown in Figure 2, cyclic voltammetry curve shows the electrochemical reversibility and the conventional 2mol/LVOSO of this solution
4+ 2mol/L H
2OSO
4Solution is approaching.The preliminary test that discharges and recharges shows that this solution can be realized charge and discharge process, and wherein single group discharge voltage can reach 1.8V.
Claims (9)
1. the electrolytic preparation method of an all vanadium ion redox flow battery electrolyte, it is characterized in that: with vanadic oxide and vanadium trioxide is primary raw material, add the organic-inorganic composite additive of proper proportion, by in electrolytic cell, carrying out the method for electrolysis, make the required electrolyte of vanadium cell, vanadium ion concentration reaches 5-6mol/L in the electrolyte; The concentration of compound additive in electrolyte is 0.1mol/L～2mol/L, and the molar ratio of organic additive and inorganic additive is (0: 1)～(8: 1) in the compound additive, wherein:
Organic additive comprise following one or more: (1) aliphatic amine compounds and aromatic polyamine compounds, and heterocyclic nitrogen compound; (2) contain aminopolycanboxylic acid's class intercalating agent compound of amino oxalic acid group; (3) sulfur heterocyclic ring compounds; (4) oxygen heterocycle compounds;
Inorganic additive comprise following one or more: the nitrate of alkali metal, alkaline-earth metal, sulfate, disulfate, bicarbonate, chloride.
2. according to the electrolytic preparation method of the described all vanadium ion redox flow battery electrolyte of claim 1, it is characterized in that: described electrolytic cell is made up of positive and negative two half-cells, two half-cells are separated by barrier film, just the electrode that inserts in half pond links to each other with the positive pole of DC power supply, and the electrode that inserts in negative half pond links to each other with the negative pole of DC power supply; During electrolysis, be sulfuric acid solution, the V of 2～5mol/L for concentration in negative half pond
2O
5And V
2O
3Powder, wherein V
2O
3And V
2O
5Mol ratio be (0: 1)～(1: 1), sulfuric acid and V
2O
5Mol ratio be (1: 1)～(2: 1), just putting in half pond and the sulfuric acid solution of negative half pond equivalent with concentration.
3. according to the electrolytic preparation method of the described all vanadium ion redox flow battery electrolyte of claim 2, it is characterized in that: positive and negative electrode adopts graphite electrode or dimensionally stable electrode, and electrolysis mode adopts constant-current electrolysis, and current density is: 20-500mA/cm
2, electrolysis time is 2～20 hours.
4. according to the electrolytic preparation method of the described all vanadium ion redox flow battery electrolyte of claim 1, it is characterized in that: V
2O
3And V
2O
5Mol ratio be (0.2: 1)-(0.8: 1).
5. according to the electrolytic preparation method of the described all vanadium ion redox flow battery electrolyte of claim 1, it is characterized in that organic additive be following one or more: ethylenediamine, diethylenetriamine, triethylene tetramine, aniline, pyridine, imidazoles, quinoline, 1, the luxuriant and rich with fragrance network quinoline of 10-, EGTA, EDTP, DTPA, EDTA, thiazole, 2-(2,4 one two basic phenyl sulfo-) benzene a pair of horses going side by side thiazole, furans, pyrans.
6. according to the electrolytic preparation method of the described all vanadium ion redox flow battery electrolyte of claim 1, it is characterized in that: the ratio of organic additive and inorganic additive is (0.5: 1)～(4: 1) in the compound additive.
7. according to the electrolytic preparation method of the described all vanadium ion redox flow battery electrolyte of claim 1, it is characterized in that: the interpolation of compound additive is constantly added in electrolyte in electrolytic process in different ways; Perhaps, before electrolysis, additive and sulfuric acid are made into mixed solution, the mixture of vanadic oxide or vanadic oxide and vanadium trioxide are dissolved in the electrolysis of carrying out in the mixed solution again, the obtained effect of these two kinds of addition manners is identical.
8. according to the electrolytic preparation method of the described all vanadium ion redox flow battery electrolyte of claim 1, it is characterized in that: in electrolysis of solutions process, add surfactant, surfactant adopts anion surfactant, cationic surfactant, non-ionic surface active agent, or wherein several mixtures, addition is the 1-5% of electrolyte weight.
9. according to the electrolytic preparation method of the described all vanadium ion redox flow battery electrolyte of claim 8, it is characterized in that: described anion surfactant is the cetyl benzene sulfonic acid sodium salt, one or more in dodecyl sodium sulfate or the sodium hexadecyl sulfate; Cationic surfactant is one or more of hexadecyltrimethylammonium chloride, softex kw or DTAB; Non-ionic surface active agent is one or more of polyethylene glycol oxide uncle octylphenol ether, polyoxyethylene nonylphenol ether or NPE.
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| CN102161757A (en) * | 2011-03-08 | 2011-08-24 | 上海树脂厂有限公司 | Special resin for vanadium extraction and preparation method thereof |
| CN102324547A (en) * | 2011-07-27 | 2012-01-18 | 四川省川威集团有限公司 | Preparation method of all-vanadium redox flow battery electrolyte |
| CN102376970A (en) * | 2010-08-11 | 2012-03-14 | 中国科学院金属研究所 | Method for preparing all-vanadium ion redox flow battery electrolyte |
| WO2012047320A1 (en) | 2010-09-28 | 2012-04-12 | Battelle Memorial Institute | Redox flow batteries based on supporting solutions containing chloride |
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