CN107887629A - Double-liquid-flow energy storage battery - Google Patents

Double-liquid-flow energy storage battery Download PDF

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Publication number
CN107887629A
CN107887629A CN201711103875.4A CN201711103875A CN107887629A CN 107887629 A CN107887629 A CN 107887629A CN 201711103875 A CN201711103875 A CN 201711103875A CN 107887629 A CN107887629 A CN 107887629A
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China
Prior art keywords
storage battery
flow energy
dual
electrolyte
battery
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CN201711103875.4A
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Chinese (zh)
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CN107887629B (en
Inventor
杨炳坤
王建业
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Sichuan Crun Power Equipment Co ltd
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Sichuan Crun Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0289—Means for holding the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
    • H01M8/2455—Grouping of fuel cells, e.g. stacking of fuel cells with liquid, solid or electrolyte-charged reactants
    • 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 a double-liquid-flow energy storage battery which is characterized in that a battery module is formed by connecting one single battery or more than two single batteries in series; a positive electrolyte storage tank, a negative electrolyte storage tank and a diaphragm; the positive electrolyte is FeSO4 aqueous solution, and the negative electrolyte is ZnSO4 aqueous solution. The invention has the advantages of rich material sources, low cost and good effect.

Description

A kind of Dual-flow energy-storage battery
Technical field
The invention belongs to flow battery technology field, more particularly to a kind of Dual-flow energy-storage battery.
Background technology
At present, Dual-flow energy-storage battery used in countries in the world, technology is most ripe, most reliable performance is " full Vanadium liquid Galvanic battery "（Jian Cheng Vanadium batteries）.Vanadium battery securities are high, long lifespan（Cycle charge-discharge number is more than 16000 times）, battery capacity Greatly, it is mainly used in peak load regulation network, such as Large Scale Wind Farm Integration, photovoltaic plant, tidal power station and thermal power station, suitable for more than 100MW's Energy-storage system.
The shortcomings that Vanadium batteries, mainly has：Positive pole liquid easily separates out vanadic anhydride precipitation when temperature is higher than 25 degrees Celsius（Vanadium Battery can easily exceed 25 degree Celsius in operation）；Wu Yangization Er Vanadium have severe toxicity, endanger environment；Graphite electrode plate is easily by positive pole liquid Etching, is just needed to be serviced for general two months；Battery cost is high, and someone calculates, and 5kw battery, cost is at 400,000 yuan More than；In addition, my state's Vanadium resources and inadequate, push away wide Vanadium batteries and are unfavorable for sustainable development.
The content of the invention
To solve the above problems, the invention provides a kind of Dual-flow energy-storage battery, more than a section monocell or two sections The battery module that cells in series forms；Anolyte liquid storage tank, cathode electrolyte storage tank, barrier film；Anode electrolyte is FeSO4 The aqueous solution, electrolyte liquid are the ZnSO4 aqueous solution.
Further, monocell is titanium plate including positive battery plate, and negative battery plates are zine plate.
Further, the positive pole and negative pole that monocell includes use three-diemsnional electrode.
Further, just extremely mesh electrode（Titanium net or acid-resistant stainless steel silk screen）, negative pole is granular electrode（Zinc granule）.
Further, positive pole reaction equation is：Fe2+ = Fe3++ e, standard electrode potential 0.77V.
Further, negative reaction formula is Zn=Zn2++ 2e, standard electrode potential are -0.763V.
Further, anode electrolyte pH value is 0.0-2.0.
Further, electrolyte liquid pH value is 2.72-5.0.
Further, additive ZnSO4 and supporting electrolyte K is contained in anode electrolyte2SO4。
Further, supporting electrolyte K is contained in electrolyte liquid2SO4。
Advantages of the present invention is：
Battery of the present invention is using iron, zinc as material, iron, Zinc material aboundresources, beneficial to sustainable development.Ferric sulfate, sulphur The abundances such as sour ferrous iron, zinc sulfate, it is cheap.Moreover, do not use proton membrane between the battery positive and negative electrode room of the present invention （Technology monopolizes for du pont company）And domestic anion-exchange membrane is used, its price is more much lower than the former.The theoretical electricity of battery Kinetic potential is 1.53 volts, 1.4 volts of Lve Gao Yu Vanadium batteries.Used positive and negative electrode electrolyte is faintly acid , Bi the strong of Vanadium battery Sulfuric acid solution（Concentration is in more than 1.8M）Corrosivity be much smaller.Electrode material titanium, or even with acid-resistant stainless steel, Inexpensive, processing cost is also low.
Embodiment
The present invention is referred to alternatively as iron zinc-anion（Exchange）Membranous type Dual-flow energy-storage battery, it is by a section monocell or two The battery module that the section above+cells in series forms.The structure of monocell is illustrated below.
Monocell includes：Anolyte liquid storage tank, cathode electrolyte storage tank, barrier film.
Anode electrolyte, i.e. positive active material, it is the FeSO4 aqueous solution, preferably contains additive ZnSO in it4, branch Hold electrolyte K2SO4.Positive pole reaction equation is：Fe2+= Fe3++ e, standard electrode potential 0.77V.Anode electrolyte pH value is 0.0—2.0。
Electrolyte liquid, i.e. negative electrode active material, it is ZnSO4The aqueous solution, it is preferred that also including electrolyte K2SO4.Negative pole Reaction equation is Zn=Zn2++ 2e, standard electrode potential are -0.763V.Electrolyte liquid pH value is 2.72-5.0.
In battery pole plates, positive plate uses titanium plate, and negative plate uses zine plate.
Barrier film between battery positive and negative electrode room uses anion（Exchange）Film.Battery theoretical electromotive force E=1.53V.
Another contribution to prior art of the present invention is：Positive pole and negative pole use a kind of form of three-diemsnional electrode：Grain Shape electrode.Just extremely mesh electrode（Titanium net or acid-resistant stainless steel silk screen）, negative pole " for granular electrode "（Zinc granule）.Use conductive particles The space being filled between positive/negative pole plate and battery diaphragm, the surface of whole conductor silk screens or grains is all electrode Surface, electrolyte between each mesh or particle space percolation and mistake, electrode reaction is carried out when flowing through（Release or Receive electronics）, so that the effective area of electrode greatly increases.Carbon cloth is also using in all-vanadium flow battery, this It is a kind of form of three-diemsnional electrode.But, this and the woven wire used in the present invention or granular electrode are entirely different 's.
Below to verifying that the experiment process of the technology of the present invention effect is illustrated.
This experiment uses imported from America anion-exchange membrane, and positive pole uses titanium sheet（The mm of d=12 mm, δ=2）Filling, bear Pole uses zinc granule（Φ= 3 mm）Filling, bed height is 8 cm.
Anode electrolyte：1000 mL beakers are taken, add appropriate distilled water, weigh Fe SO respectively4·7H2The g of O 417.2, K2SO410.9 g, ZnSO47.2 g are added thereto, and dissolving, are settled to 1000 mL, adjust pH after 1.2 or so, injection 2500 In mL liquid storage bottles.
Electrolyte liquid：1000 mL beakers are taken, appropriate distilled water is added, weighs K2SO417.4 g, ZnSO4 287.56 G is added thereto, and dissolving, is settled to 1000 mL, adjusts pH in 4.0 or so, 2500 mL liquid storage bottles of injection.
Flow battery forms：Cell body, liquid storage bottle（4）By the liquid in-out mouth of the positive and negative pole room of cell body respectively with liquid storage Bottle connection, forms flow circuits.
Charging experiment：It is 1.272 V that battery open circuit voltage is measured before charging, then flow control is left in 16.67 mL/min The right side, carry out circulation experiment.The V of charging voltage 4.0, the A of charging current 0.25, electrolyte flows to end after 1 hour, charging termination, now Battery open circuit voltage is charged to 1.34 V.Measure Fe simultaneously3+Content increases by 2.2 %.
Discharge test：The V of discharge initiation voltage 1.34, then by flow control in 16.67 mL/min or so, it is real to carry out circulation Test.After electric discharge 1 hour, cell voltage is down to 1.298 V by 1.34 V, measures Fe3+Content is down to 2 % by 2.2 %.

Claims (10)

  1. A kind of 1. Dual-flow energy-storage battery, it is characterised in that the electricity formed by a section monocell or two section above cells in series Pond module；Anolyte liquid storage tank, cathode electrolyte storage tank, barrier film；Anode electrolyte is the FeSO4 aqueous solution, electrolyte liquid For the ZnSO4 aqueous solution.
  2. 2. Dual-flow energy-storage battery as claimed in claim 1, it is characterised in that monocell is titanium including positive battery plate Plate, negative battery plates are zine plate.
  3. 3. Dual-flow energy-storage battery as claimed in claim 1, it is characterised in that the positive pole and negative pole that monocell includes use Three-diemsnional electrode.
  4. 4. Dual-flow energy-storage battery as claimed in claim 3, it is characterised in that just extremely mesh electrode, negative pole are granular electricity Pole.
  5. 5. Dual-flow energy-storage battery as claimed in claim 1, it is characterised in that positive pole reaction equation is：Fe2+ = Fe3++ e, mark Collimator electrode current potential is 0.77V.
  6. 6. Dual-flow energy-storage battery as claimed in claim 1, it is characterised in that negative reaction formula is Zn=Zn2++ 2e, mark Collimator electrode current potential is -0.763V.
  7. 7. Dual-flow energy-storage battery as claimed in claim 1, it is characterised in that anode electrolyte pH value is 0.0-2.0.
  8. 8. Dual-flow energy-storage battery as claimed in claim 1, it is characterised in that electrolyte liquid pH value is 2.72-5.0.
  9. 9. Dual-flow energy-storage battery as claimed in claim 1, it is characterised in that contain additive ZnSO4 in anode electrolyte With supporting electrolyte K2SO4。
  10. 10. Dual-flow energy-storage battery as claimed in claim 1, it is characterised in that contain supporting electrolyte in electrolyte liquid K2SO4。
CN201711103875.4A 2017-11-10 2017-11-10 Double-liquid-flow energy storage battery Active CN107887629B (en)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7332065B2 (en) * 2003-06-19 2008-02-19 Akzo Nobel N.V. Electrode
CN101619465A (en) * 2008-07-02 2010-01-06 中国科学院大连化学物理研究所 Method for preparing vanadium battery solution or adjusting capacity and special device thereof
CN102332596A (en) * 2011-08-16 2012-01-25 上海交通大学 All-iron redox energy storage cell, electrolyte of battery and preparation method of electrolyte
CN102646816A (en) * 2012-04-24 2012-08-22 中南大学 Preparing method used for flow microsphere zinc electrode of secondary zinc battery
CN102804470A (en) * 2009-06-09 2012-11-28 夏普株式会社 Redox flow battery
CN103098263A (en) * 2010-09-09 2013-05-08 加州理工学院 Electrochemical energy storage systems and methods
CN103872370A (en) * 2012-12-11 2014-06-18 苏州宝时得电动工具有限公司 Flow battery
EP2770568A1 (en) * 2013-02-26 2014-08-27 Fundacio Institut Recerca en Energia de Catalunya Electrolyte formulations for use in redox flow batteries
CN104716374A (en) * 2013-12-15 2015-06-17 中国科学院大连化学物理研究所 Neutral zinc iron double fluid flow battery
CN105474446A (en) * 2013-08-07 2016-04-06 住友电气工业株式会社 Redox flow battery

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7332065B2 (en) * 2003-06-19 2008-02-19 Akzo Nobel N.V. Electrode
CN101619465A (en) * 2008-07-02 2010-01-06 中国科学院大连化学物理研究所 Method for preparing vanadium battery solution or adjusting capacity and special device thereof
CN102804470A (en) * 2009-06-09 2012-11-28 夏普株式会社 Redox flow battery
CN103098263A (en) * 2010-09-09 2013-05-08 加州理工学院 Electrochemical energy storage systems and methods
CN102332596A (en) * 2011-08-16 2012-01-25 上海交通大学 All-iron redox energy storage cell, electrolyte of battery and preparation method of electrolyte
CN102646816A (en) * 2012-04-24 2012-08-22 中南大学 Preparing method used for flow microsphere zinc electrode of secondary zinc battery
CN103872370A (en) * 2012-12-11 2014-06-18 苏州宝时得电动工具有限公司 Flow battery
EP2770568A1 (en) * 2013-02-26 2014-08-27 Fundacio Institut Recerca en Energia de Catalunya Electrolyte formulations for use in redox flow batteries
CN105474446A (en) * 2013-08-07 2016-04-06 住友电气工业株式会社 Redox flow battery
CN104716374A (en) * 2013-12-15 2015-06-17 中国科学院大连化学物理研究所 Neutral zinc iron double fluid flow battery

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ZHIPENG XIE等: "High performance of zinc-ferrum redox flow battery with Ac-/HAc buffer solution", 《JOURNAL OF ENERGY CHEMISTRY》 *
王光信等: "《有机电合成导论》", 30 September 1997 *

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Effective date of registration: 20220510

Address after: 643000 Rongchuan Road, high tech Industrial Park, Zigong, Sichuan

Patentee after: SICHUAN CRUN POWER EQUIPMENT Co.,Ltd.

Address before: 611743 north area of Chengdu modern industrial port, Pidu District, Chengdu City, Sichuan Province

Patentee before: SICHUAN CRUN Co.,Ltd.