CN201514973U - Liquid flow battery - Google Patents

Liquid flow battery Download PDF

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Publication number
CN201514973U
CN201514973U CN2009200169870U CN200920016987U CN201514973U CN 201514973 U CN201514973 U CN 201514973U CN 2009200169870 U CN2009200169870 U CN 2009200169870U CN 200920016987 U CN200920016987 U CN 200920016987U CN 201514973 U CN201514973 U CN 201514973U
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electrolyte
battery
cathode
anode
fluid reservoir
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Expired - Fee Related
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CN2009200169870U
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Chinese (zh)
Inventor
刘建国
陈富于
陈晖�
严川伟
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Institute of Metal Research of CAS
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Institute of Metal Research of CAS
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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

Abstract

The utility model relates to the field of liquid flow batteries, particularly to a novel liquid flow battery, i.e. a vanadium/tin redox battery, which can be applied to large-scale energy storage systems. A single battery of the liquid flow battery is mainly provided with an anode, an anode liquid storage tank, a cathode and a cathode liquid storage tank, wherein the anode is separated from the cathode through a diaphragm; the anode liquid storage tank is filled with an anode electrolyte; the anode electrolyte is a vanadium-containing acid solution; the anode liquid storage tank is connected into the anode through a pipeline via a liquid pump to form a loop; the cathode liquid storage tank is filled with a cathode electrolyte; the cathode electrolyte is a tin-containing acid solution; and the cathode liquid storage tank is connected into the cathode through a pipeline via a liquid pump to form a loop. During charging and discharging, the anode electrolyte and the cathode electrolyte are driven by a liquid pump to be pumped into the battery, so that the continuous flow of the electrolytes between the liquid storage tanks and the battery is ensured; and in the liquid flow battery provided by the utility model, the electromotive force of the battery is improved, the defect of low specific energy in the battery is overcome, so that the liquid flow battery has the advantages of simple manufacturing process, low cost, long cycle life, etc..

Description

A kind of flow battery
Technical field
The utility model relates to the flow battery field, particularly a kind of novel flow 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 store energy in solution, and the capacity of this electro-chemical systems is by electrolyte storage volume and concentration of electrolyte decision, and the power of battery is by the decision of pile size.The outstanding advantage of flow battery mainly contains: the life-span is long, the reliability height, and non-pollution discharge and noise, the construction period is short, and operation and fees of maintenance are lower, are a kind of extensive efficiently electric storing 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 subjected 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.
The utility model content
Order of the present utility model is to propose a kind of novel flow battery: vanadium/tin cell, the electrode reaction VO that this flow battery positive active material takes place 2 +/ VO 2+, the electrode reaction that negative electrode active material takes place is Sn 2+/ Sn is because Sn 2+/ Sn standard electrode EMF is-0.136V that the electromotive force of forming battery is 1.136V, has improved cell emf.Simultaneously, positive active material adopts bigger tetravalence vanadium V (IV) compound of solubility, overcomes the low shortcoming of battery specific energy.In addition, abundant less than pollution and content to environment as the tin compound of electrode active material, cost is lower.
The technical solution of the utility model is as follows:
A kind of novel flow 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 anodal electrolyte is housed, anodal electrolyte is the acid solution that contains vanadium, and anodal fluid reservoir inserts the anodal loop that constitutes by pipeline via liquid pump; Negative pole electrolyte is housed in the negative pole fluid reservoir, and negative pole is the acid solution of stanniferous, and the negative pole fluid reservoir inserts negative pole by pipeline via liquid pump and constitutes the loop.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 acid solution of stanniferous, 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.
In the utility model, monocell both positive and negative polarity electrode material is conventional cellular carbon felt class material, as graphite felt, charcoal cloth, compound charcoal felt or carbon fibre composite.
Advantage of the present utility model:
1, the utility model is the flow battery positive active material with the tetravalent vanadium compound, 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 than the all-vanadium flow battery efficient height under the similarity condition.
2, the flow battery negative electrode active material is the Bivalent Tin compound in the utility model, and the Bivalent Tin compound shifts two electronics in redox reaction takes place, and the battery specific capacity is than shifting an electronics height.Simultaneously, tin compound is a kind of environment friendly material and cheap, can not pollute environment, meets the feature of flow battery environmental protection fully.
3, the utility model flow battery has that manufacturing process is simple, cost is low, the cycle life advantages of higher.
Description of drawings
Fig. 1 is the utility model single-cell structure figure.
Fig. 2 is the utility model monocell system schematic.
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 the utility model flow battery 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 the electrode frame I 3 and electrode frame II 5 outsides are installed bipolar plates I 1 and bipolar plates II 6 respectively.In the utility model, 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 the utility model flow battery 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, on this pipeline, be provided with pump I 9, fluid reservoir I 8 arrival ends are communicated with anodal 10 tops by pipeline, anodal electrolyte is housed in fluid reservoir I 8, anodal electrolyte is the acid solution that contains vanadium, and fluid reservoir I 8 inserts inside battery by pipeline via liquid pump and constitutes the loop, and the electrode reaction that takes place in fluid reservoir I 8 is VO 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, on this pipeline, be provided with pump II 13, fluid reservoir II 14 arrival ends are communicated with negative pole 11 tops by pipeline, negative pole electrolyte is housed in fluid reservoir II 14, negative pole is the acid solution of stanniferous, and fluid reservoir II 14 inserts inside battery by pipeline via liquid pump and constitutes the loop, and the electrode reaction that takes place in fluid reservoir II 14 is Sn 2++ 2e → Sn;
In positive pole 10 and the negative pole 11 electrode I 2, electrode II 12 are housed respectively, separate by barrier film 4 between positive pole 10 and the negative pole 11, in charge and discharge process, positive and negative electrode 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 utility model, organize monocell more and can be connected into pile.
Embodiment 1
In monocell negative pole fluid reservoir, add 1mol/L divalent tin ion (stannous oxide) and 2mol/L sulfuric acid electrolyte as negative pole electrolyte, in the anodal fluid reservoir of monocell, add 2mol/L tetravalent vanadium ion (vanadic sulfate) and 2mol/L sulfuric acid electrolyte as anodal electrolyte.Graphite felt is an electrode material, and cation-exchange membrane is a 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.
Embodiment 2
In monocell negative pole fluid reservoir, add 1mol/L divalent tin ion (stannous hydroxide) and 2mol/L sulfuric acid electrolyte as negative pole electrolyte, in the anodal fluid reservoir of monocell, add 2mol/L tetravalent vanadium ion (vanadic sulfate) and 2mol/L sulfuric acid electrolyte as anodal electrolyte.Graphite felt is an electrode material, and cation-exchange membrane is a 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%.
Embodiment 3
In monocell negative pole fluid reservoir, add 1mol/L divalent tin ion (stannous chloride) and 2mol/L sulfuric acid electrolyte as negative pole electrolyte, in the anodal fluid reservoir of monocell, add 2mol/L tetravalent vanadium ion (vanadium dioxide) and 2mol/L sulfuric acid electrolyte as anodal electrolyte.Graphite felt is an electrode material, and cation-exchange membrane is a 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%.
Embodiment 4
In monocell negative pole fluid reservoir, add 0.5mol/L divalent tin ion (stannous sulfide) and 2.5mol/L sulfuric acid electrolyte as negative pole electrolyte, in the anodal fluid reservoir of monocell, add 1mol/L tetravalent vanadium ion (vanadic sulfate) and 2.5mol/L sulfuric acid electrolyte as anodal electrolyte.Graphite felt is an electrode material, and cation-exchange membrane is a 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
In monocell negative pole fluid reservoir, add 0.5mol/L divalent tin ion (stannous pyrophosphate) and 2.5mol/L sulfuric acid electrolyte as negative pole electrolyte, in the anodal fluid reservoir of monocell, add 1mol/L tetravalent vanadium ion (vanadium dioxide) and 2.5mol/L sulfuric acid electrolyte as anodal electrolyte.Graphite felt is an electrode material, and cation-exchange membrane is a 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
In monocell negative pole fluid reservoir, add 0.5mol/L divalent tin ion (stannous sulfate) and 2.5mol/L sulfuric acid electrolyte as negative pole electrolyte, in the anodal fluid reservoir of monocell, add 1mol/L tetravalent vanadium ion (vanadic sulfate) and 2.5mol/L sulfuric acid electrolyte as anodal electrolyte.Graphite felt is an electrode material, and cation-exchange membrane is a 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 (3)

1. flow battery, it is characterized in that, 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 anodal electrolyte is housed, anodal electrolyte is the acid solution that contains vanadium, and anodal fluid reservoir inserts the anodal loop that constitutes by pipeline via liquid pump; Negative pole electrolyte is housed in the negative pole fluid reservoir, and negative pole is the acid solution of stanniferous, and the negative pole fluid reservoir inserts negative pole by pipeline via liquid pump and constitutes the loop.
2. according to the described flow battery of claim 1, it is characterized in that, organize monocell more and be connected into pile.
3. according to the described flow battery of claim 1, it is characterized in that barrier film adopts cation-exchange membrane.
CN2009200169870U 2009-08-27 2009-08-27 Liquid flow battery Expired - Fee Related CN201514973U (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102709579A (en) * 2012-04-05 2012-10-03 深圳市金钒能源科技有限公司 Method for preparing vanadium liquid
CN101997129B (en) * 2009-08-27 2013-09-18 中国科学院金属研究所 Liquid 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
CN109103484A (en) * 2018-08-29 2018-12-28 深圳大学 A kind of flow battery and preparation method thereof
CN111653799A (en) * 2020-07-16 2020-09-11 盐城工学院 Pretreatment method of tin cathode of tin-based alkaline flow battery
CN114263567A (en) * 2021-12-08 2022-04-01 广东力恒新能源科技有限公司 Iron-chromium liquid flow energy storage battery system

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101997129B (en) * 2009-08-27 2013-09-18 中国科学院金属研究所 Liquid flow battery
CN102709579A (en) * 2012-04-05 2012-10-03 深圳市金钒能源科技有限公司 Method for preparing vanadium liquid
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
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
CN109103484A (en) * 2018-08-29 2018-12-28 深圳大学 A kind of flow battery and preparation method thereof
CN111653799A (en) * 2020-07-16 2020-09-11 盐城工学院 Pretreatment method of tin cathode of tin-based alkaline flow battery
CN111653799B (en) * 2020-07-16 2022-03-15 盐城工学院 Pretreatment method of tin cathode of tin-based alkaline flow battery
CN114263567A (en) * 2021-12-08 2022-04-01 广东力恒新能源科技有限公司 Iron-chromium liquid flow energy storage battery system
CN114263567B (en) * 2021-12-08 2024-04-02 广东力恒新能源科技有限公司 Iron-chromium liquid flow energy storage battery system

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Granted publication date: 20100623

Termination date: 20150827

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