CN102881931A - Phosphorus-containing all-vanadium redox flow battery anode electrolyte - Google Patents
Phosphorus-containing all-vanadium redox flow battery anode electrolyte Download PDFInfo
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- CN102881931A CN102881931A CN2012103651185A CN201210365118A CN102881931A CN 102881931 A CN102881931 A CN 102881931A CN 2012103651185 A CN2012103651185 A CN 2012103651185A CN 201210365118 A CN201210365118 A CN 201210365118A CN 102881931 A CN102881931 A CN 102881931A
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- electrolyte
- phosphorus
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- vanadium
- flow battery
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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 belongs to the technical field of large-scale energy storage redox flow batteries, and especially relates to a phosphorus-containing all-vanadium redox flow battery anode electrolyte. The phosphorus-containing all-vanadium redox flow battery anode electrolyte comprises a phosphorus-containing additive which is one or more than one of orthophosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, and its potassium salts or sodium salts; the using amount of the phosphorus-containing additive is 0.005%-5.0% of the amount of substance of vanadium. According to the invention, the phosphorus-containing compound is used as the additive, which reduces the polarization phenomenon of redox reaction of the anode electrolyte on the electrode surface; on one hand, the reaction impedance of the electrolyte of the electrode surface is reduced; and the improvement of the charge and discharge capacity is realized; on the other hand, the overcharge phenomenon of the electrolyte at a high potential is effectively prevented, and the stable operation of the electrolyte is realized. The preparation process of the invention is simple in operation, energy-saving, environment-friendly, and low in cost, and can realize the stable operation of the electrolyte in the battery.
Description
Technical field
The invention belongs to scale energy-storage liquid galvanic battery technical field, particularly a kind of phosphorous positive electrolyte for all-vanadiumredox flow battery.
Background technology
The traditional energy undersupply is the key factor of the present socio-economic development of restriction, and the new energy technologies such as wind energy and solar energy are because its renewable characteristics are in widespread attention.At present, new energy technology can occupy certain proportion in energy output, and this ratio will continue to strengthen along with development simultaneously.But wind energy and solar power generation have intermittent characteristics, have become the Main Bottleneck of its development of restriction.Vanadium redox battery (all vanadium redox flow battery, be called for short: all-vanadium flow battery)) but have that the large degree of depth of electrical power storage amount discharges and recharges, characteristics such as long service life, easy to operate and maintenance, can be used in the level and smooth output of the regenerative resources such as wind energy, solar energy, realize the peak load shifting of electrical network.
All-vanadium flow battery is to realize conversion between electric energy and the chemical energy by the valent variation of vanadium.It mainly comprises: the critical materials such as electrolyte, proton exchange membrane, electrode, bipolar plates.Electrolyte is one of core component of all-vanadium flow battery.Both positive and negative polarity electrolyte is respectively by V
4+/ V
5+And V
2+/ V
3+V occurs to forming in electricity in the anode electrolyte during charging
4+To V
5+Transform V in the negative pole electrolyte
3+To V
2+Transform, the hydrionic generation of simultaneous, during discharge in contrast.Along with the continuous increase of new forms of energy market to the energy-storage battery demand, therefore in unit volume, exist more active material to become the focus of research.But the researcher finds, gradually raising along with vanadium ion concentration in the electrolyte, when concentration during greater than 1.8 mol/L or operating temperature when being higher than 50 ℃, anode electrolyte can be separated out pentavalent vanadium compound in the charging process, this compound can be attached to the graphite felt electrode surface, when adhesion amount acquires a certain degree, graphite felt can occur and stop up, cause whole vanadium cell to work.So, under prescribed concentration, how to improve the activity of vanadium ion in the electrolyte, so that more vanadium ion participates in the redox reaction, realize that taking full advantage of of active material is the emphasis of research.
Chinese invention patent 200510075608 discloses a kind of electrolyte, wherein contain the additives such as sodium pyrophosphate, sodium sulphate, the adding of these additives can realize the stability of electrolyte, but can't improve V electrolyte in the catalytic activity of graphite felt electrode surface.Chinese invention patent 200910259740.6 discloses electrolyte of vanadium redox battery and the vanadium cell that contains additive, wherein additive comprises 2-mercaptobenzothiazole and diphenylguanidine, cyclic voltammetry shows that additive can improve the anode and cathode peak current, and charge-discharge test shows that the adding of additive can significantly improve the charge/discharge capacity of electrolyte simultaneously.But the adding that cyclic voltammetry shows additive is unfavorable for the long-term use of electrolyte to the invertibity of electrolyte oxidation reduction reaction and stability variation all.
Summary of the invention
Not enough for prior art, the invention provides a kind of phosphorous positive electrolyte for all-vanadiumredox flow battery, to reach the purpose of all-vanadium flow battery efficient stable operation.
A kind of phosphorous positive electrolyte for all-vanadiumredox flow battery, it comprises phosphor-included additive, and described phosphor-included additive is one or more in orthophosphoric acid, metaphosphoric acid, phosphorous acid and hypophosphorous acid and sylvite or the sodium salt; The consumption of described phosphor-included additive be vanadium amount of substance 0.005%～5.0%.
The consumption of described phosphor-included additive be vanadium amount of substance 0.01%～2.0%.
Beneficial effect of the present invention is:
The present invention has used phosphorus-containing compound as additive, the polarization phenomena of anode electrolyte in the electrode surface redox reaction have been reduced, reduce electrolyte at the electrode surface reaction impedance on the one hand, realize the raising of charge/discharge capacity, can effectively prevent on the other hand the overcharge phenomenon of electrolyte under high potential, realize the stable operation of electrolyte.Preparation technology of the present invention is simple to operate, energy-conserving and environment-protective, cost are low, can realize the stable operation of electrolyte in battery simultaneously.
Description of drawings
Fig. 1 adds the electrolyte of phosphorous acid additive and the electrokinetic potential scanning curve of blank electrolysis liquid among the embodiment 1;
Fig. 2 is the comparison diagram that discharges and recharges that adds the electrolyte of phosphorous acid additive and blank electrolysis liquid among the embodiment 1.
Embodiment
The invention provides a kind of phosphorous positive electrolyte for all-vanadiumredox flow battery, the present invention will be further described below in conjunction with the drawings and specific embodiments.
The present invention introduces a class phosphorus-containing compound as additive in anode electrolyte of vanadium battery.The adding of this additive can improve the charge/discharge capacity of electrolyte, realizes the stable operation of battery-efficient.This is because containing the phosphide additive can significantly improve anode electrolyte at the chemical property of electrode surface redox reaction, reduces the polarization phenomena of cell reaction.
The additive that is used for the object of the invention is: one or more of orthophosphoric acid, metaphosphoric acid, phosphorous acid and hypophosphorous acid and sylvite thereof or sodium salt.
Other composition that is suitable for the electrolyte of vanadium redox battery among the present invention can adopt VOSO
4-H
2SO
4System, VOSO
4Concentration be 0.5 mol/L ~ 5 mol/L, H
2SO
4Concentration be 1 mol/L ~ 6 mol/L, the preferable range of concentration is VOSO
4Concentration be 1 mol/L ~ 3 mol/L, H
2SO
4Concentration be 2 mol/L ~ 4 mol/L.
Be suitable for the phosphorous acid among the present invention, be dissolved in advance in the capacity electrolyte, the time is 0.5 h ~ 3 h.
Being applicable to electrode material of the present invention can be polyacrylonitrile-radical graphite felt electrode, graphite electrode or carbon paper electrode.
The consumption that is used for phosphor-included additive of the present invention be generally the electrolyte vanadium amount 0.005%～5.0%, usually, this consumption be preferably vanadium in the electrolyte amount 0.01%～2.0%.
Embodiment 1
VOSO with certain content
4Be dissolved in the sulfuric acid solution, make 60 ml 2M VOSO
4+ 3M H
2SO
4Anodal stoste, in mentioned solution, in batches, slowly add 0.098 g phosphorous acid, fully make anode electrolyte after the stirring and dissolving.Do not add the above-mentioned electrolyte of additive as negative pole electrolyte with 60 mL.The reaction electrode of all-vanadium flow battery is 80 cm
2The graphite felt electrode, significantly improve through graphite felt electrode activity after the acid heat processing, barrier film adopts the cation proton exchange membrane, after hydrogen peroxide and sulfuric acid removal of impurities and connecting the active group processing, the container that both positive and negative polarity electrolyte will be housed respectively is connected with the all-vanadium flow battery assembly, adopt the pump circulation to consist of the electrolyte circulation loop, form dynamic all-vanadium flow battery, obtain battery 1.
The operation of repeated experiments example 1, difference are not add any additive, obtain battery 2.
Embodiment 2
Adopt the pentavalent vanadium solution of standby 2 mol/L of electrolyte legal system, add in the 15 ml pentavalent vanadium solutions respectively and account for vanadium amount of substance 0.5%, 1.0% and 2.0% phosphorous acid, abundant mixing and stirring, be positioned in 60 ℃ the baking oven, be divided into observing time: observe immediately, 7 days, 15 days, 30 days, fully shake during each the observation, until the electrolyte state is put into baking oven when constant again.
The operation of repeated experiments example 1, difference are not add in the pentavalent V electrolyte any additive.
By electrochemistry experiment the blank electrolysis liquid that obtains and the electrokinetic potential scanning curve that adds additive electrolyte, as shown in Figure 1.VOSO in the electrolyte wherein
4Concentration be 2 mol/L, H
2SO
4Concentration be 3 mol/L, add the phosphorous acid account for vanadium amount of substance 1.0%.Compare the electrolyte that does not add additive, electrolyte significantly reduced at the self-potential of electrode surface electrochemical reaction after phosphorous acid added, show under the equipolarization electric current, the potential value that contains additive electrolyte is lower, in the charging process, the time that reaches charge cutoff voltage will prolong, thereby be conducive to realize significantly improving of electrolyte capacity.Contrast two scanning curves, can find out clearly, behind the interpolation phosphorous acid, there is a platform area in electrolyte between current potential 0.1 V ~ 0.8 V, this will be conducive to realize reducing electrolyte in the polarization of electrode surface, so that more multi-energy is used for electrochemical reaction, thereby improve battery efficiency.
Fig. 2 is the charging and discharging curve of battery 1 and battery 2, and as seen from the figure, the adding of phosphorous acid can significantly improve the time that discharges and recharges of battery under the unitary current density, shows that the adding of additive can significantly improve the charge storage ability of electrolyte.Compare two charging and discharging curves, when charging voltage during near the cut-ff voltage of battery, it is more level and smooth obviously to draw the curve that adds phosphorous acid, and polarization resistance significantly reduces, and its result is obviously consistent with Fig. 1.Compare battery 2, the charge/discharge capacity of battery 1 improves respectively 44.54% and 44.03%, shows that the interpolation of phosphorous acid can significantly improve the performance of electrolyte, realizes the operation of all-vanadium flow battery high-performance.
The mechanism of action of additive is researcher's research emphasis always, but the under extreme conditions stability of self of additive has been ignored in a lot of researchs, when additive lost efficacy in charging process, will cause the electrolyte charge storage ability to descend, thereby cause battery performance significantly to be decayed.In order further to inquire into the electrolyte high-temperature stability, because the pentavalent vanadium solution is easy to produce a large amount of precipitations under the high temperature, this is conducive to the further investigated additive to the impact of electrolyte precipitation, adopts embodiment 2, and the result is as shown in table 1.
Table 1. different content additive is to electrolyte stability influence information slip
Table 1 has been showed the impact of different content additive on high temperature (60 ℃) anode electrolyte stability.As seen from table, when additive adds electrolyte, the color of electrolyte changes immediately, illustrated the vanadium ion in the electrolyte probably with the state of phosphorous acid complexing Cheng Xin, when pentavalent electrolyte as for high temperature lower time, As time goes on, the amount that precipitates in the electrolyte is reducing gradually, this adding that shows phosphorous acid has remarkable effect to the precipitation that hinders electrolyte, this is because behind the state of phosphorous acid and vanadium ion complexing Cheng Xin, significantly reduced the pentavalent vanadium and changed into the generation of vanadic oxide coagulation reaction, thereby realized that the electrolyte high temperatures exists.This result has quite strong directive function to the operation of electrolyte under the high temperature, is conducive to simultaneously guarantee at high temperature operation steady in a long-term of vanadium cell.
Claims (2)
1. phosphorous positive electrolyte for all-vanadiumredox flow battery, it is characterized in that: comprise phosphor-included additive, described phosphor-included additive is one or more in orthophosphoric acid, metaphosphoric acid, phosphorous acid and hypophosphorous acid and sylvite or the sodium salt; The consumption of described phosphor-included additive be vanadium amount of substance 0.005%～5.0%.
2. a kind of phosphorous positive electrolyte for all-vanadiumredox flow battery according to claim 1 is characterized in that: the consumption of described phosphor-included additive be vanadium amount of substance 0.01%～2.0%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103280591A (en) * | 2013-05-25 | 2013-09-04 | 成都赢创科技有限公司 | Method for manufacturing solid electrolyte for vanadium flow battery |
| CN103490086A (en) * | 2013-09-03 | 2014-01-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of vanadium electrolyte |
| CN104300168A (en) * | 2013-07-18 | 2015-01-21 | 中国科学院大连化学物理研究所 | Inorganic ammonium phosphate-containing positive electrode electrolyte for whole vanadium flow battery |
| CN105322207A (en) * | 2014-07-30 | 2016-02-10 | 中国科学院大连化学物理研究所 | Phosphorous heteropoly acid all-vanadium redox flow battery positive electrolyte and application thereof |
| CN105762395A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院大连化学物理研究所 | All-vanadium redox flow battery positive electrolyte containing composite additive and application thereof |
| 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 |
| CN108199068A (en) * | 2018-01-09 | 2018-06-22 | 中国工程物理研究院电子工程研究所 | A kind of low temperature all-vanadium redox flow battery electrolyte and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103280591A (en) * | 2013-05-25 | 2013-09-04 | 成都赢创科技有限公司 | Method for manufacturing solid electrolyte for vanadium flow battery |
| CN104300168A (en) * | 2013-07-18 | 2015-01-21 | 中国科学院大连化学物理研究所 | Inorganic ammonium phosphate-containing positive electrode electrolyte for whole vanadium flow battery |
| CN103490086A (en) * | 2013-09-03 | 2014-01-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Preparation method of vanadium electrolyte |
| CN105322207A (en) * | 2014-07-30 | 2016-02-10 | 中国科学院大连化学物理研究所 | Phosphorous heteropoly acid all-vanadium redox flow battery positive electrolyte and application thereof |
| CN105322207B (en) * | 2014-07-30 | 2018-04-06 | 中国科学院大连化学物理研究所 | A kind of phosphorous heteropoly acid positive electrolyte for all-vanadiumredox flow battery and its application |
| CN105762395A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院大连化学物理研究所 | All-vanadium redox flow battery positive electrolyte containing composite additive and application thereof |
| CN105762395B (en) * | 2014-12-16 | 2018-06-19 | 中国科学院大连化学物理研究所 | A kind of positive electrolyte for all-vanadiumredox flow battery containing compound additive and its application |
| 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 |
| CN108199068A (en) * | 2018-01-09 | 2018-06-22 | 中国工程物理研究院电子工程研究所 | A kind of low temperature all-vanadium redox flow battery electrolyte and preparation method thereof |
| 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 |
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Application publication date: 20130116 |