CN103000926A - Electrolyte of vanadium battery - Google Patents
Electrolyte of vanadium battery Download PDFInfo
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- CN103000926A CN103000926A CN2012105375423A CN201210537542A CN103000926A CN 103000926 A CN103000926 A CN 103000926A CN 2012105375423 A CN2012105375423 A CN 2012105375423A CN 201210537542 A CN201210537542 A CN 201210537542A CN 103000926 A CN103000926 A CN 103000926A
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- vanadium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides an electrolyte of a vanadium battery. An ionic liquid is introduced into the electrolyte. The ionic liquid enables vanadium ions in the electrolyte to be not easy to precipitate; and conductivity of the electrolyte and redox reversibility of the vanadium ions are increased; so that an electrochemical polarization degree can be reduced; and battery capacity and energy efficiency are increased. In a specific embodiment, the electrolyte is mainly composed of the vanadium ions, sulfuric acid and the ionic liquid.
Description
Technical field
The present invention relates to secondary cell, be specifically related to electrolyte of vanadium redox battery.
Background technology
Vanadium redox battery has that energy conversion efficiency is high, capacity can adjusting, long service life, high security and advantages of environment protection, is mainly used in the supporting energy storage device of electricity generation system of the regenerative resources such as solar energy, wind energy, peak-clipping and valley-filling device and uninterrupted power supply and the emergency power system of electrical network.
In vanadium cell, the energy content of battery stores with the electrolyte form, and it is comprised of vanadium ion and sulfuric acid, and positive pole is by VO
2+/ VO
2+Oxidation-reduction pair forms, and negative pole is by V
3+/ V
2+The group oxidation-reduction pair forms.The concentration that improves electrolyte is to improve the effective way of the specific energy of battery.But because vanadium has vacant d track, not only easily be combined with ligand, also very easily associate between the vanadium atom.Concentration is larger, and degree of association is larger.Complicated ions is participated in electrochemical reaction, and corresponding reaction energy barrier increases, and causes polarization to increase, and reaction speed is slow.And the raising of concentration will inevitably increase resistance, viscosity of electrolyte etc.Simultaneously, pentavalent vanadium ion solubility is little, and the positive solution of high concentration can be separated out red vanadate precipitation near fully charged state the time, may stop up the porous electrode surface, causes battery to use.Research shows that also trivalent and divalent vanadium ion also easily precipitate at low temperatures, and stability of this explanation negative pole electrolyte also has problems.
The method that increases at present the stability of vanadium solution mainly comprises the raising solution acidity and adds two kinds of additives.The too high corrosion that can accelerate battery component of solution acidity improves the requirement to material.And anticathode electrolyte, because the cause of common-ion effect, the acidity increase can reduce the solubility of Low Valent Vanadium ion on the contrary.Therefore, the scheme to electrolyte introducing additive is extensively studied.
Existing report adds inorganic salts or organic substance etc. in the electrolyte and improves its stability or active, for example CN1507103A discloses a kind of electrolyte of high stability, be in the sulfuric acid solution of vanadic sulfate, add in alkali metal salt, hydroxyl material or the surfactant at least a, because the coordinative role between the additive combination, the precipitation of establishment pentavalent vanadium and the oxidation of bivalent vanadium have improved the stability of electrolyte.CN1598063A discloses and a kind ofly adds Na in vanadic sulfate solution
2SO
4, the additive such as polyoxyethylene nonylphenol ether method improve its stability.Na
2SO
4After the excessive adding, because common-ion effect can be impelled separating out of vanadium ion.And polyoxyethylene nonylphenol ether is easily oxidized and ineffective under strong oxidizing condition, thereby reduces its stability.CN1719655A disclose a kind of with sulfuric acid, hydrate alcohol as supporting electrolyte, and the method for adding the stabilizers such as sodium sulphate, sodium pyrophosphate, prodan or hydrogen peroxide work in the electrolyte improves electrolyte stability.Analyze as can be known, although ethanol can reduce solution viscosity, improve stability and the conductive capability of solution, in charge and discharge process, ethanol makes the Efficiency Decreasing of battery easily by the oxidation of high valence state vanadium, thereby the method remains further to be improved.CN1507103 discloses and has a kind ofly added the stabilizers such as alcohols, organic acid and inorganic acid, salt or macromolecular compound in V electrolyte, it is said that can to make vanadium ion stable under high concentration, but this does not provide the data of result of use aspect.Can predict, organic substance wherein also has by the V5+ oxidation, produce CO2, cause both positive and negative polarity pressure imbalance and conductivity descends, electrolyte viscosity increases problem, inorganic metal salt wherein can cause the hydration of going of vanadium oxygen hydrated ion in the solution, is unfavorable for the problem of vanadium dissolving.
Therefore, prior art still needs to explore the stability that more effective method improves electrolyte of vanadium redox battery.
Summary of the invention
The objective of the invention is to propose a kind of new electrolyte of vanadium redox battery, to improve the stability of vanadium ion.
Other purpose of the present invention is to improve the conductivity of electrolyte of vanadium redox battery and the activity of vanadium ion.
Introduced ionic liquid as additive in the electrolyte of vanadium redox battery of the present invention.This ionic liquid has improved the conductivity of electrolyte and the redox invertibity of vanadium ion so that the vanadium ion in the electrolyte is difficult for separating out, thereby reduces electrochemical polarization, also improves in addition battery capacity and energy efficiency.
In embodiment, electrolyte of the present invention mainly is comprised of vanadium ion, sulfuric acid and ionic liquid.
Further, wherein the concentration of vanadium ion is 2-3M.
Further, the concentration of sulfuric acid is 3.0-5.0M.
In embodiment, the addition of ionic liquid is the 0.1-3.0% of electrolyte in mass.
The cation that consists of described ionic liquid can be from quaternary ammonium cation quaternary phosphine cation, glyoxaline cation, pyridylium, the guanidine cationoid, choline type cation, the pyrrolidines cation moiety, the triazole cation, the pyrazoles cation, the thiazole cation, the anion that consists of described ionic liquid is selected from the tetrafluoro boric acid anion, the hexafluoro acid anion, the acetic acid anion, the trifluoroacetic acid anion, ethyl sulfuric acid ester anion, the methyl sulfate anion, the pyrovinic acid anion, the trifluoromethane sulfonic acid anion, trifluoromethyl sulphamide anion, pentafluoroethyl group sulphamide anion, trifluoroacetyl fluoroform sulfonamide anions.
Preferably, described ionic liquid is to be selected from 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-methylimidazole mesylate, 1-butyl-3-methylimidazole fluoroform sulphonate, 1-butyl-3-vinyl imidazole tetrafluoroborate, 1-ethyl-3-methylimidazole tetrafluoroborate, 1-dodecyl-3-methylimidazole mesylate, one or more in 1-hexyl-3-methylimidazole mesylate.
Description of drawings
Fig. 1 be among the embodiment 1 vanadium cell 1 and vanadium cell 2 discharge and recharge volt-ampere curve figure.
Embodiment
Ionic liquid claims again the room temperature fuse salt, is comprised of the yin, yang ion fully.In ionic compound, the active force between the zwitterion is the Coulomb force, and its size is relevant with amount of charge and the radius of zwitterion, and ionic radius is larger, and the active force between them is less, and the fusing point of this ionic compound is just lower.The yin, yang ion volume that consists of ion liquid compound is very large, loosely organized, causes the active force between them lower, to such an extent as at room temperature be liquid, can be used as solvent or medium, not volatile and burning.The present inventor attempts introducing ionic liquid in electrolyte of vanadium redox battery, attempts to explore ionic liquid and whether the performance of electrolyte is produced favorable influence.Found that, the adding of ionic liquid can obviously improve the stability of vanadium ion, so that vanadium ion is separated out in being difficult for from electrolyte system.
The salt that ionic liquid is comprised of organic cation and inorganic anion, can be used for organic cation of the present invention and include but not limited to quaternary ammonium cation, quaternary phosphine cation, glyoxaline cation, pyridylium, guanidine cationoid, choline type cation, pyrrolidines cation moiety, triazole cation, pyrazoles cation, thiazole cation, wherein preferably use quaternary ammonium cation, quaternary phosphine cation, glyoxaline cation, pyridylium.Can be used for inorganic anion of the present invention and include but not limited to the tetrafluoro boric acid anion, the hexafluoro acid anion, the acetic acid anion, the trifluoroacetic acid anion, ethyl sulfuric acid ester anion, the methyl sulfate anion, the pyrovinic acid anion, the trifluoromethane sulfonic acid anion, trifluoromethyl sulphamide anion, pentafluoroethyl group sulphamide anion, trifluoroacetyl fluoroform sulfonamide anions etc., preferably use and do not have the anion of reproducibility, for example a tetrafluoro boric acid anion, the hexafluoro acid anion, the acetic acid anion, the trifluoroacetic acid anion, ethyl sulfuric acid ester anion etc.
In exemplary embodiments of the present invention, the ionic liquid that uses is to be selected from 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-methylimidazole mesylate, 1-butyl-3-methylimidazole fluoroform sulphonate, 1-butyl-3-vinyl imidazole tetrafluoroborate, 1-ethyl-3-methylimidazole tetrafluoroborate, 1-dodecyl-3-methylimidazole mesylate, the mixture of one or more in 1-hexyl-3-methylimidazole mesylate.
Can align, bear electrolyte and use identical ionic liquid.As preferably, can select different ionic liquids for the heterogeneity of positive and negative electrode electrolyte.For example, have the characteristics of certain oxidizability for pentavalent vanadium in the anode electrolyte, use the irreducibility ionic liquid.If electrolyte uses at low temp area, can select those broad application temperature range, have a low-viscosity ionic liquids especially at low temperatures.
In exemplary embodiment of the present invention, electrolyte is comprised of vanadium ion, sulfuric acid and ionic liquid.The total concentration of vanadium ion can be 1.5-3M, usually in the scope of 2-3M.The concentration of sulfuric acid is preferably 3.0-5.0M.In the exemplary embodiment, the addition of glyoxaline ion liquid is the 0.1-3.0% of electrolyte in mass.
The below exemplifies explanation technical scheme of the present invention with specific embodiment, and these examples should not be construed as limitation of the present invention.
Embodiment 1:
Full vanadium cell 1:
Battery number: 1
Barrier film: perfluorinated sulfonic acid ion exchange membrane
Collector: conducting polymer composite
Electrode material: carbon felt
Electrolyte: anodal liquid is the CV(IV) for 2.0mol/L, CH2SO4 are 3.0mol/L, contain the electrolyte of 0.3%1-butyl-3-methylimidazole fluoroform sulphonate (BMIMOTF), negative pole liquid is the CV(III) be 3.0mol/L, contain the electrolyte of 0.3%1-butyl-3-methylimidazole fluoroform sulphonate (BMIMOTF) for 2.0mol/L, CH2SO4.
Full vanadium cell 2:
Battery number and material etc. are all identical with 1, and only electrolyte is different;
Anodal liquid is the CV(IV) for 2.0mol/L, CH2SO4 are the electrolyte of 3.0mol/L, negative pole liquid is the CV(III) be that 2.0mol/L, CH2SO4 are the electrolyte of 3.0mol/L.Full vanadium cell 1 and full vanadium cell 2 have been carried out charging and discharging performance test, and Fig. 1 has showed the volt-ampere curve of this charge-discharge test.The red line that wherein voltage is lower in the charging curve represents the volt-ampere curve of vanadium cell 1, and the black line that voltage is higher represents the volt-ampere curve of vanadium vanadium cell 2.Put the volt-ampere curve that voltage is higher in the point curve red line represents full vanadium cell 1, the black line that voltage is lower represents the volt-ampere curve of full vanadium cell 2.
As can be seen from Figure 1, use the battery 1 contain il electrolyte with as the battery 2 of blank relatively, shown lower charging voltage and higher put a little in pressure, battery 1 has also shown higher battery capacity.
Embodiment 2:
V electrolyte 1: negative pole liquid is the CV(III) be 3.0mol/L, contain the electrolyte of 0.3% 1-butyl-3-methylimidazole fluoroform sulphonate (BMIMOTF) for 2.0mol/L, CH2SO4.V electrolyte 2: negative pole liquid is the CV(III) be that 2.0mol/L, CH2SO4 are the electrolyte of 3.0mol/L.V electrolyte 1 and V electrolyte 2 have carried out the conductivity contrast test, and V electrolyte 1 its conductivity is improved, and its test data is as shown in table 1.
Table 1 is the conductivity value of blank electrolysis liquid and additive electrolyte
Embodiment 3:
V electrolyte 1: electrolyte is the CV(V) be 3.0mol/L, contain the electrolyte of 0.3%1-butyl-3-methylimidazole fluoroform sulphonate (BMIMOTF) for 2.0mol/L, CH2SO4.V electrolyte 2: electrolyte is the CV(V) be that 2.0mol/L, CH2SO4 are the electrolyte of 3.0mol/L.V electrolyte 1 and V electrolyte 2 respectively under 40 ° of C, 45 ° of C, 50 ° of C constant temperature place, investigate electrolyte and separate out situation, its test data is as shown in table 2.
The investigation of the blank pentavalent vanadium solution of table 2 and the stability of additive pentavalent vanadium solution under different temperatures
Example 4, V electrolyte 1: electrolyte is CV(III I/ IV) (the III/ IV is than being 1:1) be 3.0mol/L, contain the electrolyte of 0.3%1-butyl-3-methylimidazole fluoroform sulphonate (BMIMOTF) for 2.0mol/L, CH2SO4.V electrolyte 2: electrolyte is CV(III/IV) (III/IV is than being 1:1) be the electrolyte of 3.0mol/L for 2.0mol/L, CH2SO4.V electrolyte 1 and V electrolyte are carried out viscosity test.Result's demonstration, the adding of ion liquid addictive there is no impact to the viscosity of electrolyte, its test data is as shown in table 3.
The viscosity number of table 3 blank electrolysis liquid and additive electrolyte
Abovely in conjunction with embodiment and specific embodiment design of the present invention is set forth.Those skilled in the art are easy to expect above-mentioned ins and outs are changed or improve after obtaining instruction of the present invention, for example can carry out selection or the MOLECULE DESIGN of ionic liquid, make it be more suitable for general the application or the application of special occasions.It also may be adjusted or improve other compositions of electrolyte.These all should be included within claims limited range.
Claims (7)
1. an electrolyte of vanadium redox battery is characterized in that comprising ionic liquid as additive.
2. electrolyte of vanadium redox battery as claimed in claim 1 is characterized in that, mainly is comprised of vanadium ion, sulfuric acid and ionic liquid.
3. electrolyte of vanadium redox battery as claimed in claim 1, wherein, the concentration of vanadium ion is 2.0-3.0M.
4. electrolyte of vanadium redox battery as claimed in claim 1, wherein, the concentration of sulfuric acid is 3.0-5.0M.
5. electrolyte of vanadium redox battery as claimed in claim 1, wherein, the addition of described ionic liquid is the 0.1-3.0% of electrolyte in mass.
6. such as each described electrolyte of vanadium redox battery of claim 1 to 5, wherein, the cation that consists of described ionic liquid is selected from quaternary ammonium cation quaternary phosphine cation, glyoxaline cation, pyridylium, the guanidine cationoid, choline type cation, the pyrrolidines cation moiety, the triazole cation, the pyrazoles cation, the thiazole cation, the anion that consists of described ionic liquid is selected from the tetrafluoro boric acid anion, the hexafluoro acid anion, the acetic acid anion, the trifluoroacetic acid anion, ethyl sulfuric acid ester anion, the methyl sulfate anion, the pyrovinic acid anion, the trifluoromethane sulfonic acid anion, trifluoromethyl sulphamide anion, pentafluoroethyl group sulphamide anion, trifluoroacetyl fluoroform sulfonamide anions.
7. electrolyte of vanadium redox battery as claimed in claim 6, wherein, described ionic liquid is to be selected from 1-butyl-3-methyl imidazolium tetrafluoroborate, 1-butyl-3-methylimidazole mesylate, 1-butyl-3-methylimidazole fluoroform sulphonate, 1-butyl-3-vinyl imidazole tetrafluoroborate, 1-ethyl-3-methylimidazole tetrafluoroborate, 1-dodecyl-3-methylimidazole mesylate, one or more in 1-hexyl-3-methylimidazole mesylate.
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| CN2012105375423A CN103000926A (en) | 2012-12-12 | 2012-12-12 | Electrolyte of vanadium battery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105322186A (en) * | 2014-07-30 | 2016-02-10 | 中国科学院大连化学物理研究所 | Method for reducing electrochemical polarization of all-vanadium redox flow battery |
| CN106410249A (en) * | 2016-11-11 | 2017-02-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium battery positive electrolyte and method for improving stability of vanadium battery positive electrolyte |
| CN106450509A (en) * | 2015-08-05 | 2017-02-22 | 苏州宝时得电动工具有限公司 | Electrolyte and battery |
| WO2019054947A1 (en) * | 2017-09-14 | 2019-03-21 | National University Of Singapore | A condensed phase aqueous redox flow battery |
| CN110400970A (en) * | 2019-06-04 | 2019-11-01 | 江西力能新能源科技有限公司 | A kind of electrolyte and its application in High Temperature Lithium Cell |
| CN111477925A (en) * | 2020-06-08 | 2020-07-31 | 雅安市中甫新能源开发有限公司 | Additive for preparing high-concentration vanadium battery electrolyte and preparation method |
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| US20040241552A1 (en) * | 2001-05-18 | 2004-12-02 | Maria Skyllas-Kazacos | Vanadium redox battery electrolyte |
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2012
- 2012-12-12 CN CN2012105375423A patent/CN103000926A/en active Pending
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| US20040241552A1 (en) * | 2001-05-18 | 2004-12-02 | Maria Skyllas-Kazacos | Vanadium redox battery electrolyte |
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| 张倩: "丁腈橡胶复合物抗静电性能及丁腈橡胶基聚合物固体电解质材料的研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105322186A (en) * | 2014-07-30 | 2016-02-10 | 中国科学院大连化学物理研究所 | Method for reducing electrochemical polarization of all-vanadium redox flow battery |
| CN105322186B (en) * | 2014-07-30 | 2018-06-19 | 中国科学院大连化学物理研究所 | A kind of method for reducing all-vanadium flow battery activation polarization |
| CN106450509A (en) * | 2015-08-05 | 2017-02-22 | 苏州宝时得电动工具有限公司 | Electrolyte and battery |
| CN106410249A (en) * | 2016-11-11 | 2017-02-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium battery positive electrolyte and method for improving stability of vanadium battery positive electrolyte |
| WO2019054947A1 (en) * | 2017-09-14 | 2019-03-21 | National University Of Singapore | A condensed phase aqueous redox flow battery |
| CN110400970A (en) * | 2019-06-04 | 2019-11-01 | 江西力能新能源科技有限公司 | A kind of electrolyte and its application in High Temperature Lithium Cell |
| CN110400970B (en) * | 2019-06-04 | 2023-09-05 | 江西力能新能源科技有限公司 | Electrolyte material and application thereof in high-temperature lithium battery |
| CN111477925A (en) * | 2020-06-08 | 2020-07-31 | 雅安市中甫新能源开发有限公司 | Additive for preparing high-concentration vanadium battery electrolyte and preparation method |
| CN111477925B (en) * | 2020-06-08 | 2023-01-10 | 雅安市中甫新能源开发有限公司 | Additive for preparing high-concentration vanadium battery electrolyte and preparation method |
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Application publication date: 20130327 |