CN107887629B - Double-liquid-flow energy storage battery - Google Patents

Double-liquid-flow energy storage battery Download PDF

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Publication number
CN107887629B
CN107887629B CN201711103875.4A CN201711103875A CN107887629B CN 107887629 B CN107887629 B CN 107887629B CN 201711103875 A CN201711103875 A CN 201711103875A CN 107887629 B CN107887629 B CN 107887629B
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battery
electrolyte
energy storage
positive
negative
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CN107887629A (en
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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

Double-liquid-flow energy storage battery
Technical Field
The invention belongs to the technical field of flow batteries, and particularly relates to a double-flow energy storage battery.
Background
At present, the most mature technology and the most reliable performance of the dual-fluid energy storage battery used in all countries in the world are the "all-vanadium-blade fluid battery" (called a "vanadium battery for short). The safety of vanadium battery is high, and is longe-lived (the circulation charge-discharge number of times is greater than 16000 times), and battery capacity is big, mainly used electric wire netting peak shaving, like large-scale wind-powered electricity generation field, photovoltaic power plant, morning and evening tides power station and thermal power station, be applicable to the energy storage system more than 100 MW.
The disadvantages of the battery in the tank are: vanadium pentoxide precipitates are easy to separate out when the temperature of the positive pole liquid is higher than 25 ℃ (the vanadium pentoxide precipitates can easily exceed 25 ℃ in the operation of the vanadium battery); the vanadium pentoxide has strong toxicity and harms the environment; the graphite polar plate is easy to be etched by the anode liquid and needs to be maintained for two months generally; the cost of the battery is high, and is calculated by people, and the cost of the battery with 5kw is more than 40 ten thousand yuan; in addition, the vanadium resources in China are insufficient, and the popularization of the vanadium battery is not beneficial to the continuous development.
Disclosure of Invention
In order to solve the problems, the invention provides a double-liquid-flow energy storage battery, which is a battery module 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.
Furthermore, the single cell comprises a positive cell plate which is a titanium plate, and a negative cell plate which is a zinc plate.
Further, the single cell comprises a positive electrode and a negative electrode which are three-dimensional electrodes.
Further, the positive electrode is a mesh electrode (titanium mesh or acid-resistant stainless steel mesh), and the negative electrode is a granular electrode (zinc granules).
Further, the positive reaction formula is: fe2+ = Fe3++ e, standard electrode potential 0.77V.
Further, the negative electrode reaction formula is Zn = Zn2++ 2e, standard electrode potential-0.763V.
Further, the pH value of the positive electrolyte is 0.0-2.0.
Further, the pH value of the negative electrode electrolyte is 2.72-5.0.
Furthermore, the positive electrolyte contains additive ZnSO4 and supporting electrolyte K2SO4。
Further, the negative electrode electrolyte contains a supporting electrolyte K2SO4。
The invention has the advantages that:
the battery provided by the invention adopts iron and zinc as materials, and the iron and zinc materials are rich in resources and beneficial to sustainable development. The ferric sulfate, ferrous sulfate, zinc sulfate and the like have rich sources and low prices. Moreover, the price of the battery of the invention is much lower than that of the battery of the invention which adopts a domestic anion exchange membrane instead of a proton membrane (the technology is monopolized by DuPont company in the United states). The theoretical electromotive force of the battery is 1.53 volts, which is slightly higher than 1.4 volts of the battery in the vanadium blade. The positive and negative electrode electrolytes used are both weakly acidic and much less corrosive than the strong sulfuric acid solution (concentration of 1.8M or more) of the vanadium battery. The electrode material is made of titanium, even acid-resistant stainless steel, and has low price and low processing cost.
Detailed Description
The invention can be called as Fe-Zn-anion (exchange) membrane type double-liquid-flow energy storage battery, which is a battery module formed by connecting one single battery or more than two single batteries in series. The structure of the single cell will be explained below.
The battery cell includes: a positive electrolyte storage tank, a negative electrolyte storage tank and a diaphragm.
The positive electrode electrolyte, i.e., the positive electrode active material, is an aqueous FeSO4 solution, preferably containing an additive ZnSO therein4Supporting electrolyte K2SO4. The positive reaction formula is: fe2+= Fe3++ e, standard electrode potential 0.77V. The pH value of the positive electrolyte is 0.0-2.0.
The negative electrode electrolyte, i.e., the negative electrode active material, is ZnSO4The aqueous solution preferably also comprises an electrolyte K2SO4. The negative reaction formula is Zn = Zn2++ 2e, standard electrode potential-0.763V. The pH value of the negative electrode electrolyte is 2.72-5.0.
In the battery polar plate, the positive plate adopts a titanium plate, and the negative plate adopts a zinc plate.
The separator between the positive and negative electrode chambers of the battery adopts an anion (exchange) membrane. The theoretical electromotive force E = 1.53V of the battery.
Another contribution of the present invention to the prior art is: both the positive and negative electrodes take the form of three-dimensional electrodes: a granular electrode. The positive electrode is a mesh electrode (a titanium mesh or an acid-resistant stainless steel mesh), and the negative electrode is a granular electrode (zinc granules). The space between the positive/negative electrode plate and the battery diaphragm is filled with conductor particles, the surfaces of all conductor wire meshes or particle particles are the surfaces of the electrodes, and electrolyte flows through the gaps among the meshes or particles and flows through the gaps to carry out electrode reaction (release or accept electrons), so that the effective area of the electrode is greatly increased. Carbon fiber cloth is also used in all vanadium flow batteries, which is also a form of three-dimensional electrode. However, this is quite different from the wire mesh or granular electrodes used in the present invention.
The following is an example of a test procedure for verifying the technical effect of the present invention.
In the experiment, an anion exchange membrane imported from America is adopted, the positive electrode is filled with titanium sheets (d =12 mm, = 2 mm), the negative electrode is filled with zinc particles (phi = 3 mm), and the bed height is 8 cm.
Anode electrolyte: taking 1000 mL beaker, adding appropriate amount of distilled water, and respectively weighing Fe SO4·7H2O 417.2 g，K2SO4 10.9 g ，ZnSO4Adding 7.2 g of the mixture into the solution, dissolving, diluting to 1000 mL, adjusting the pH to about 1.2, and injecting into a 2500 mL solution storage bottle.
And (3) cathode electrolyte: taking 1000 mL beaker, adding appropriate amount of distilled water, and weighing K2SO4 17.4 g，ZnSO4287.56 g of the extract was added thereto, and the mixture was dissolved, diluted to 1000 mL, adjusted to pH 4.0 or so, and poured into a 2500 mL liquid storage bottle.
Flow battery composition: the battery body and the liquid storage bottles (4) are respectively connected with the liquid inlet and outlet of the positive and negative electrode chambers of the battery body and the liquid storage bottles to form a flowing loop.
Charging experiment: before charging, the open-circuit voltage of the battery is measured to be 1.272V, and then the flow rate is controlled to be about 16.67 mL/min, and a circulation experiment is carried out. The charging voltage is 4.0V, the charging current is 0.25A, the electrolyte is drained after 1 hour, the charging is terminated, and the open-circuit voltage of the battery is charged to 1.34V. At the same time measure Fe3+The content is increased by 2.2%.
Discharge experiment: the discharge initiation voltage was 1.34V, and the flow rate was controlled to about 16.67 mL/min, and a cycle experiment was performed. After discharging for 1 hour, the cell voltage is reduced from 1.34V to 1.298V, and Fe is measured3+The content is reduced from 2.2 percent to 2 percent.

Claims (7)

1. A double-liquid-flow energy storage battery is characterized in that the double-liquid-flow energy storage battery is a battery module formed by connecting one single battery or more than two single batteries in series; the single cell comprises a positive electrolyte storage tank, a negative electrolyte storage tank, a positive electrode, a negative electrode and a diaphragm; the positive electrolyte is FeSO4Aqueous solution, negative electrode electrolyte ZnSO4An aqueous solution;
the anode is a three-dimensional mesh electrode, and the cathode is a three-dimensional granular electrode;
the pH value of the positive electrolyte is 0.0-2.0;
the diaphragm is an anion exchange membrane.
2. The bi-fluid energy storage battery of claim 1, wherein the single cell further comprises a positive battery plate and a negative battery plate, the positive battery plate being a titanium plate and the negative battery plate being a zinc plate.
3. The bi-fluid energy storage cell of claim 1, wherein the positive electrode reaction formula is: fe2+ = Fe3++ e, standard electrode potential 0.77V.
4. The bi-fluid energy storage battery of claim 1, wherein the negative electrode reaction formula is Zn = Zn2++ 2e, standard electrode potential-0.763V.
5. The bi-flow energy storage cell of claim 1, wherein the negative electrolyte has a pH of 2.72 to 5.0.
6. The bi-fluid energy storage cell of claim 1, wherein the positive electrolyte comprises an additive of ZnSO4And a supporting electrolyte K2SO4。
7. The bi-fluid energy storage battery of claim 1 wherein the negative electrolyte contains a supporting electrolyte K2SO4。
CN201711103875.4A 2017-11-10 2017-11-10 Double-liquid-flow energy storage battery Active CN107887629B (en)

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CN107887629B true CN107887629B (en) 2020-11-20

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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
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

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US7332065B2 (en) * 2003-06-19 2008-02-19 Akzo Nobel N.V. Electrode
CN102646816B (en) * 2012-04-24 2014-08-27 中南大学 Preparing method used for flow microsphere zinc electrode of secondary zinc battery

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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
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

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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.