CN101997129B - Liquid flow battery - Google Patents
Liquid flow battery Download PDFInfo
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- CN101997129B CN101997129B CN2009100134486A CN200910013448A CN101997129B CN 101997129 B CN101997129 B CN 101997129B CN 2009100134486 A CN2009100134486 A CN 2009100134486A CN 200910013448 A CN200910013448 A CN 200910013448A CN 101997129 B CN101997129 B CN 101997129B
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- 239000007788 liquid Substances 0.000 title claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 14
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012530 fluid Substances 0.000 claims description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- 230000004888 barrier function Effects 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 239000007773 negative electrode material Substances 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 10
- 238000005341 cation exchange Methods 0.000 claims description 8
- 238000003411 electrode reaction Methods 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 6
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 5
- 150000003606 tin compounds Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 4
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 3
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 claims description 3
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 claims description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- -1 alkyl sulfonic acid Chemical compound 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 claims description 2
- 229960002799 stannous fluoride Drugs 0.000 claims description 2
- 150000003682 vanadium compounds Chemical class 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000007772 electrode material Substances 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910001432 tin ion Inorganic materials 0.000 description 6
- 229910001456 vanadium ion Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- Y02E60/10—Energy storage using batteries
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of liquid flow batteries, and particularly relates to a novel liquid flow battery, i.e., a vanadium/tin battery that can be applied to a large-scale energy storage system. A battery cell of the liquid flow battery is mainly provided with an anode, an anode liquid reservoir, a cathode and a cathode liquid reservoir, wherein the anode and the cathode are separatedby a spectrum; the anode liquid reservoir is filled with anode electrolyte which is an acid solution containing vanadium; the anode liquid reservoir is connected to the anode from a liquid pump through a pipeline to form a loop; the cathode liquid reservoir is filled with cathode electrolyte which is an acid solution containing tin; and the cathode liquid reservoir is connected to the cathode from a liquid pump through a pipeline to form a loop. In the charging and discharging process, the anode and cathode electrolyte are respectively pumped to the battery under the push of the liquid pumps so as to ensure that the electrolyte flows continuously between the liquid reservoirs and the battery. The liquid flow battery improves the electromotive force of the battery, overcomes the defect of low battery specific energy and has the advantages of simple manufacturing process, low cost, long cycle life, and the like.
Description
Technical field
The present invention relates to the flow battery field, particularly a kind of New galvanic battery: vanadium/tin cell, this battery can be applicable to large-scale energy-storage system.
Background technology
Redox flow batteries is a kind of with the electro-chemical systems of energy storage in solution, and the capacity of this electro-chemical systems is determined by electrolyte storage volume and concentration of electrolyte, and the power of battery is determined by the pile size.The outstanding advantages of flow battery mainly contains: the life-span is long, and reliability is high, non-pollution discharge and noise, and the construction period is short, and operation and fees of maintenance are lower, are a kind of efficient large scale storage electrical energy devices.
Nineteen eighty-two D-G.Oei proposes to use SnCl
2Make the flow battery negative electrode active material, V
2O
5As the positive active material of flow battery, some performance change of battery have been studied.But because V
2O
5Be slightly soluble in water, the solubility in acid solution is less, causes concentration of electrolyte lower, and the battery specific energy is subject to the restriction of concentration of electrolyte.Simultaneously, anode electrode reaction VO
2 +/ VO
2+Standard electrode EMF is 1.00V, negative electrode reaction Sn
4+/ Sn
2+Standard electrode EMF is 0.154V, and forming cell emf is 0.846V.
Summary of the invention
Order of the present invention is to propose a kind of New galvanic battery: vanadium/tin cell, the electrode reaction VO that this flow battery positive active material occurs
2 +/ VO
2+, the electrode reaction that negative electrode active material occurs is Sn
2+/ Sn is because Sn
2+/ Sn standard electrode EMF is-0.136V that the electromotive force that forms battery is 1.136V, has improved cell emf.Simultaneously, positive active material adopts larger tetravalence vanadium V (IV) compound of solubility, overcomes the low shortcoming of battery specific energy.In addition, as the tin compound of electrode active material environment is not polluted and rich content, cost is lower.
Technical scheme of the present invention is as follows:
A kind of New galvanic battery: vanadium/tin cell, the monocell of this flow battery mainly is provided with positive pole, anodal fluid reservoir, negative pole, negative pole fluid reservoir, positive and negative electrode is separated by barrier film, in the anodal fluid reservoir anode electrolyte is housed, anode electrolyte is the acid solution that contains vanadium, and anodal fluid reservoir consists of the loop by pipeline via liquid pump access positive pole; Negative electricity solution liquid is housed in the negative pole fluid reservoir, and negative pole is stanniferous acid solution, and the negative pole fluid reservoir consists of the loop by pipeline via liquid pump access negative pole.In charge and discharge process, both positive and negative polarity electrolyte pumps into electrolyte in the battery respectively under liquid pump promotes, and guarantees that electrolyte constantly flows between fluid reservoir and battery.
In the stanniferous acid solution, mainly be that the concentration range of the negative electrode active material aqueous solution is 0.01mol/L～2mol/L with stannous oxide, stannous hydroxide, stannous chloride, stannous sulfide, stannous pyrophosphate, stannous sulfate, the inferior tin of alkyl sulfonic acid or the stannous fluoride negative electrode active material as monocell.
Containing in the acid solution of vanadium, mainly is that the concentration range of the positive active material aqueous solution is 0.01mol/L～4mol/L with vanadium dioxide or the vanadic sulfate positive active material as monocell.
Electrolyte is acidic electrolysis bath, in this electrolyte acid main component be following one or more: sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, carbonic acid, the concentration range of electrolyte are 0.1mol/L～5mol/L.
Barrier film can prevent the cross pollution of both positive and negative polarity electrolyte, can pass through proton again simultaneously, and barrier film can adopt conventional cation-exchange membrane.
Among the present invention, monocell both positive and negative polarity electrode material is conventional cellular carbon felt class material, such as graphite felt, charcoal cloth, composite carbon felt or carbon fibre composite.
Advantage of the present invention:
1, the present invention is take tetravalent vanadium compound as the flow battery positive active material, Bivalent Tin is the flow battery negative electrode active material, and battery is through charge-discharge test, has to have extended cycle life, but the advantage of deep discharge, battery efficiency is higher than the all-vanadium flow battery efficient under the similarity condition.
2, the flow battery negative electrode active material is the Bivalent Tin compound among the present invention, and the Bivalent Tin compound shifts two electronics in redox reaction occurs, and the battery specific capacity is higher than shifting an electronics.Simultaneously, tin compound is a kind of environment friendly material and cheap, can to environment, not meet the feature of flow battery environmental protection fully.
3, flow battery of the present invention has that manufacturing process is simple, cost is low, the cycle life advantages of higher.
Description of drawings
Fig. 1 is single-cell structure figure of the present invention.
Fig. 2 is monocell system schematic of the present invention.
Among Fig. 1-Fig. 2,1 bipolar plates I; 2 electrode I; 3 electrode frame I; 4 barrier films; 5 electrode frame II; 6 bipolar plates II; 7 monocells; 8 fluid reservoir I; 9 pump I; 10 positive poles; 11 negative poles; 12 electrode II; 13 pump II; 14 fluid reservoir II.
Embodiment
As shown in Figure 1, the monocell 7 of New galvanic battery of the present invention mainly comprises: bipolar plates I 1, electrode I 2, electrode frame I 3, barrier film 4, electrode frame II 5, bipolar plates II 6 etc., electrode I 2 and electrode II are installed on respectively in electrode frame I 3 and the electrode frame II 5, electrode frame I 3 and electrode frame II 5 inboards separate by barrier film 4, and bipolar plates I 1 and bipolar plates II6 are installed respectively in electrode frame I 3 and electrode frame II 5 outsides.Among the present invention, monocell positive and negative electrode bipolar plates is conventional conducing composite material, conduction carbon plate or metallic plate.
As shown in Figure 2, the monocell system of New galvanic battery of the present invention mainly comprises electrode I 2, barrier film 4, fluid reservoir I 8, pump I 9, positive pole 10, negative pole 11, electrode II 12, pump II 13, fluid reservoir II 14 etc., and concrete structure is as follows:
Fluid reservoir I 8 is anodal fluid reservoir, fluid reservoir I 8 ports of export are communicated with anodal 10 bottoms by pipeline, be provided with pump I 9 at this pipeline, fluid reservoir I 8 arrival ends are communicated with anodal 10 tops by pipeline, in fluid reservoir I 8, anode electrolyte is housed, anode electrolyte is the acid solution that contains vanadium, and fluid reservoir I 8 consists of the loop by pipeline via liquid pump access inside battery, is VO in the electrode reaction of fluid reservoir I 8 interior generations
2 ++ 2H
++ e → VO
2++ H
2O;
Fluid reservoir II 14 is the negative pole fluid reservoir, fluid reservoir II 14 ports of export are communicated with negative pole 11 bottoms by pipeline, be provided with pump II 13 at this pipeline, fluid reservoir II 14 arrival ends are communicated with negative pole 11 tops by pipeline, negative electricity solution liquid is housed in fluid reservoir II 14, negative pole is stanniferous acid solution, and fluid reservoir II 14 consists of the loop by pipeline via liquid pump access inside battery, is Sn in the electrode reaction of fluid reservoir II 14 interior generations
2++ 2e → Sn;
Embodiment 1
Add 1mol/L divalent tin ion (stannous oxide) and 2mol/L sulfuric acid electrolyte in the monocell negative pole fluid reservoir as negative pole electrolyte, adding 2mol/L tetravalent vanadium ion (vanadic sulfate) and 2mol/L sulfuric acid electrolyte are as anode electrolyte in the anodal fluid reservoir of monocell.Graphite felt is electrode material, and cation-exchange membrane is barrier film, and battery is carried out charge-discharge test.Wherein, charging and discharging currents density is 50mA/cm
2, charging voltage is 1.5V, discharge voltage is 1.1V.Through charge-discharge test repeatedly, average voltage efficient is 88%, average coulombic efficiency 94.85%, average energy efficient 83.24%.The efficient that is higher than all-vanadium flow battery under the similarity condition.
Add 1mol/L divalent tin ion (stannous hydroxide) and 2mol/L sulfuric acid electrolyte in the monocell negative pole fluid reservoir as negative pole electrolyte, adding 2mol/L tetravalent vanadium ion (vanadic sulfate) and 2mol/L sulfuric acid electrolyte are as anode electrolyte in the anodal fluid reservoir of monocell.Graphite felt is electrode material, and cation-exchange membrane is barrier film, and battery is carried out charge-discharge test.Wherein, charging and discharging currents density is 100mA/cm
2, charging voltage is 1.5V, discharge voltage is 1.1V.Through charge-discharge test repeatedly, average voltage efficient is 83.7%, average coulombic efficiency 94.4%, average energy efficient 79.1%.
Add 1mol/L divalent tin ion (stannous chloride) and 2mol/L sulfuric acid electrolyte in the monocell negative pole fluid reservoir as negative pole electrolyte, adding 2mol/L tetravalent vanadium ion (vanadium dioxide) and 2mol/L sulfuric acid electrolyte are as anode electrolyte in the anodal fluid reservoir of monocell.Graphite felt is electrode material, and cation-exchange membrane is barrier film, and battery is carried out charge-discharge test.Wherein, charging and discharging currents density is 160mA/cm
2, charging voltage is 1.5V, discharge voltage is 1.1V.Through charge-discharge test repeatedly, average voltage efficient is 75.6%, average coulombic efficiency 92.5%, average energy efficient 69.9%.
Add 0.5mol/L divalent tin ion (stannous sulfide) and 2.5mol/L sulfuric acid electrolyte in the monocell negative pole fluid reservoir as negative pole electrolyte, adding 1mol/L tetravalent vanadium ion (vanadic sulfate) and 2.5mol/L sulfuric acid electrolyte are as anode electrolyte in the anodal fluid reservoir of monocell.Graphite felt is electrode material, and cation-exchange membrane is barrier film, and battery is carried out charge-discharge test.Wherein, charging and discharging currents density is 50mA/cm
2, charging voltage is 1.5V, discharge voltage is 1.1V.Through charge-discharge test repeatedly, average voltage efficient is 87.8%, average coulombic efficiency 95.7%, average energy efficient 84.1%.
Embodiment 5
Add 0.5mol/L divalent tin ion (stannous pyrophosphate) and 2.5mol/L sulfuric acid electrolyte in the monocell negative pole fluid reservoir as negative pole electrolyte, adding 1mol/L tetravalent vanadium ion (vanadium dioxide) and 2.5mol/L sulfuric acid electrolyte are as anode electrolyte in the anodal fluid reservoir of monocell.Graphite felt is electrode material, and cation-exchange membrane is barrier film, and battery is carried out charge-discharge test.Wherein, charging and discharging currents density is 100mA/cm
2, charging voltage is 1.5V, discharge voltage is 1.1V.Through charge-discharge test repeatedly, average voltage efficient is 85.2%, average coulombic efficiency 92.6%, average energy efficient 78.9%.
Embodiment 6
Add 0.5mol/L divalent tin ion (stannous sulfate) and 2.5mol/L sulfuric acid electrolyte in the monocell negative pole fluid reservoir as negative pole electrolyte, adding 1mol/L tetravalent vanadium ion (vanadic sulfate) and 2.5mol/L sulfuric acid electrolyte are as anode electrolyte in the anodal fluid reservoir of monocell.Graphite felt is electrode material, and cation-exchange membrane is barrier film, and battery is carried out charge-discharge test.Wherein, charging and discharging currents density is 160mA/cm
2, charging voltage is 1.5V, discharge voltage is 1.1V.Through charge-discharge test repeatedly, average voltage efficient is 77.5%, average coulombic efficiency 92.1%, average energy efficient 71.4%.
Claims (6)
1. flow battery, it is characterized in that, the monocell of this flow battery is provided with positive pole, anodal fluid reservoir, negative pole, negative pole fluid reservoir, positive and negative electrode is separated by barrier film, in the anodal fluid reservoir anode electrolyte is housed, anode electrolyte is the acid solution that contains vanadium, and anodal fluid reservoir consists of the loop by pipeline via liquid pump access positive pole; Negative electricity solution liquid is housed in the negative pole fluid reservoir, and negative pole electrolyte is stanniferous acid solution, and the negative pole fluid reservoir consists of the loop by pipeline via liquid pump access negative pole;
Negative pole electrolyte is comprised of the negative electrode active material aqueous solution and acidic electrolysis bath, and anode electrolyte is comprised of the positive active material aqueous solution and acidic electrolysis bath;
The flow battery positive active material is tetravalent vanadium compound, and the electrode reaction that positive active material occurs is VO
2 +/ VO
2+The flow battery negative electrode active material is the Bivalent Tin compound, and the electrode reaction that negative electrode active material occurs is Sn
2+/ Sn;
The concentration range of the negative electrode active material aqueous solution is 0.01mol/L～2mol/L; The concentration range of the positive active material aqueous solution is 0.01mol/L～4mol/L; The concentration range of described acidic electrolysis bath is 0.1mol/L～5mol/L.
2. according to flow battery claimed in claim 1, it is characterized in that, organize monocell more and be connected into pile.
3. according to flow battery claimed in claim 1, it is characterized in that, in the stanniferous acid solution, active material is stannous oxide, stannous hydroxide, stannous chloride, stannous sulfide, stannous pyrophosphate, stannous sulfate, the inferior tin of alkyl sulfonic acid or stannous fluoride.
4. according to flow battery claimed in claim 1, it is characterized in that, contain in the acid solution of vanadium, active material is vanadium dioxide or vanadic sulfate.
5. according to flow battery claimed in claim 1, it is characterized in that, in the described acidic electrolysis bath acid composition be following one or more: sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, carbonic acid.
6. according to flow battery claimed in claim 1, it is characterized in that, barrier film adopts cation-exchange membrane.
Priority Applications (1)
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|---|---|---|---|
| CN2009100134486A CN101997129B (en) | 2009-08-27 | 2009-08-27 | Liquid flow battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100134486A CN101997129B (en) | 2009-08-27 | 2009-08-27 | Liquid flow battery |
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| CN101997129A CN101997129A (en) | 2011-03-30 |
| CN101997129B true CN101997129B (en) | 2013-09-18 |
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| CN2009100134486A Expired - Fee Related CN101997129B (en) | 2009-08-27 | 2009-08-27 | Liquid flow battery |
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| CN102244286B (en) * | 2011-06-07 | 2014-10-15 | 中国东方电气集团有限公司 | Flow battery system and repair device thereof |
| CN102856573A (en) * | 2011-06-30 | 2013-01-02 | 中国科学院大连化学物理研究所 | Zinc-vanadium redox flow energy storage battery |
| CN102447132A (en) * | 2011-10-24 | 2012-05-09 | 吉林省晋吉锂电池有限公司 | Semisolid flow lithium ion battery |
| CN102709579B (en) * | 2012-04-05 | 2015-08-19 | 天津滨海储能技术有限公司 | The preparation method of vanadium liquid |
| CN103928720A (en) * | 2013-03-26 | 2014-07-16 | 摩尔动力(北京)技术股份有限公司 | Method for prolonging working time length of liquid change storage battery |
| CN104518233A (en) * | 2013-09-29 | 2015-04-15 | 中国科学院大连化学物理研究所 | Chlorine-containing all-vanadium redox flow battery anode electrolyte |
| JP2017054631A (en) * | 2015-09-08 | 2017-03-16 | 昭和電工株式会社 | Electrolytic solution for redox flow battery, and redox flow battery |
| CN106328975A (en) * | 2016-11-11 | 2017-01-11 | 攀钢集团攀枝花钢铁研究院有限公司 | Full-vanadium oxidation reduction flow battery |
| CN106299437A (en) * | 2016-11-11 | 2017-01-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Vanadium cell and electrolyte liquid thereof and the method improving its electro-chemical activity |
| WO2019054332A1 (en) * | 2017-09-14 | 2019-03-21 | 東洋エンジニアリング株式会社 | Redox flow battery |
| CN108199069B (en) * | 2018-01-17 | 2020-09-29 | 大连博融新材料有限公司 | Electrolyte for redox flow battery and preparation method thereof |
| CN109103484A (en) * | 2018-08-29 | 2018-12-28 | 深圳大学 | A kind of flow battery and preparation method thereof |
| CN110649304B (en) * | 2019-09-25 | 2024-08-16 | 何国珍 | Tin-iodic acid rechargeable battery |
| CN110993999A (en) * | 2019-11-26 | 2020-04-10 | 中国科学院金属研究所 | Electrolyte containing additive for iron-chromium flow battery and application thereof |
| CN113707925A (en) * | 2021-08-24 | 2021-11-26 | 复旦大学 | Tin-manganese aqueous flow battery |
| CN117254074B (en) * | 2023-11-20 | 2024-02-09 | 华中科技大学 | Alkaline tin negative electrode electrolyte and alkaline tin-iron flow battery |
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| D-G.OEI.Chemically regenerative redox fuel cells.《JOURNAL OF APPLIED ELECTROCHEMISTRY》.1982,第12卷(第1期),87-100. |
| D-G.OEI.Chemically regenerative redox fuel cells.《JOURNAL OF APPLIED ELECTROCHEMISTRY》.1982,第12卷(第1期),87-100. * |
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