CN111261910B - Positive electrode electrolyte for alkaline zinc-iron flow battery and application - Google Patents

Positive electrode electrolyte for alkaline zinc-iron flow battery and application Download PDF

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Publication number
CN111261910B
CN111261910B CN201811458602.6A CN201811458602A CN111261910B CN 111261910 B CN111261910 B CN 111261910B CN 201811458602 A CN201811458602 A CN 201811458602A CN 111261910 B CN111261910 B CN 111261910B
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electrolyte
positive
flow battery
positive electrode
alkaline zinc
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CN111261910A (en
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段寅琦
李先锋
袁治章
张华民
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Bodisun New Energy Science & Technology Co ltd
Dalian Institute of Chemical Physics of CAS
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Bodisun New Energy Science & Technology Co ltd
Dalian Institute of Chemical Physics of CAS
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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
    • H01M8/08—Fuel cells with aqueous electrolytes
    • H01M8/083—Alkaline fuel cells
    • 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
    • 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 relates to a positive electrolyte for an alkaline zinc-iron flow battery and application thereof. Compared with the original positive electrolyte prepared only from ferrocyanide salt, the positive electrolyte has higher active substance concentration and lower cation activity, the higher active substance concentration can effectively improve the conductivity of the electrolyte, so that the cycle performance and the efficiency of the battery are improved, and the charge-discharge capacity and the energy density of the battery are greatly improved; the lower cation activity can reduce the osmotic pressure of the electrolyte, inhibit the migration of the positive and negative electrolytes and further improve the long-time cycle stability of the battery.

Description

Positive electrode electrolyte for alkaline zinc-iron flow battery and application
Technical Field
The invention relates to a positive electrolyte for an alkaline zinc-iron flow battery, a preparation method of the positive electrolyte and application of the positive electrolyte in the alkaline zinc-iron flow battery.
Background
The flow battery is a new electrochemical energy storage technology, and compared with other energy storage technologies, the flow battery has the advantages of high energy conversion efficiency, flexible system design, large storage capacity, free site selection, deep discharge, safety, environmental protection, low maintenance cost and the like, and can be widely applied to the aspects of power generation and energy storage of renewable energy sources such as wind energy, solar energy and the like, emergency power supply systems, standby power stations, power systems and the like, and peak clipping and valley filling are realized. The alkaline zinc-iron flow battery is considered to be a flow battery with high development potential due to the advantages of high safety, good stability, long service life (the service life is more than 15 years), low cost and the like.
The electrolyte of the anode and the cathode of the battery is an important component of the flow battery, and plays the roles of storing energy, conducting a circuit and converting electric energy into chemical energy. The concentration of active substances in the electrolyte, the conductivity of the electrolyte and the like directly influence the charge-discharge capacity and the battery performance of the battery; therefore, the electrolyte is required to have higher active material concentration and conductivity, and also to have better chemical stability and lower cost. Most of the positive electrolyte used by the alkaline zinc-iron flow battery at home and abroad is prepared from a single active substance, although the chemical stability of the positive electrolyte is excellent, the active substance in the electrolyte is low, so that the charge-discharge capacity and the conductivity of the battery are low, the cost of the electrolyte in the alkaline zinc-iron flow battery is indirectly increased, and the industrial prospect of the flow battery of the system is limited. Meanwhile, the active substance di and/or ferric cyanide complex in the positive electrolyte has a large amount of alkali metal or alkaline earth metal cations, so that the osmotic pressure of the positive electrolyte is far higher than that of the negative electrolyte, the migration of the positive electrolyte and the negative electrolyte is serious when the battery runs for a long time, and the stability of the battery under the long-time running condition is influenced. Therefore, it is important to develop a positive electrode electrolyte having high concentration, high conductivity, and low osmotic pressure.
In the process of dissolving the ionic compound in water, anions and cations with equal charges are dissociated. The saturation solubility in water is determined by the product of the concentrations of anions and cations, i.e., the solubility product constant Ksp. Ksp is determined by the type of cation and anion, and at a certain temperature, if the solubility of a specific ion is to be improved, the concentration of the corresponding ion is to be reduced.
Disclosure of Invention
The invention aims to overcome the problems of the existing positive electrolyte for the alkaline zinc-iron flow battery and provides a novel positive electrolyte for the alkaline zinc-iron flow battery. The concentration and the conductivity of active substances in the electrolyte can be greatly improved under the condition of not obviously reducing the stability of the electrolyte, and the osmotic pressure of the electrolyte is reduced, so that the positive electrolyte which is extremely low in cost, excellent in performance and suitable for the alkaline zinc-iron flow battery is obtained.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides an additive for positive electrolyte of an alkaline zinc-iron flow battery, which is at least one of crown ether substances or cryptand compounds, wherein the crown ether substances comprise one or more than two of 15-crown (ether) -5, 18-crown (ether) -6, 12-crown (ether) -4 or dicyclohexyl-18-crown (ether) -6; the cryptand compound includes [2.2.2] -cryptand.
The invention also provides a positive electrode electrolyte for the alkaline zinc-iron flow battery, which comprises the additive; the molar concentration of the additive in the positive electrolyte is 0.01-2 mol/L.
Preferably, the positive electrode electrolyte contains one or more of sodium ions, potassium ions and lithium ions as cations, and contains divalent and/or trivalent iron cyanide complexes and hydroxide ions as anions.
Preferably, the divalent and/or trivalent iron cyanide complex is ferricyanide (Fe (CN))6 3-) Or ferrocyanide (Fe (CN)6 4-) One or two of them.
Preferably, the concentration of the divalent and/or trivalent iron cyanide complex in the positive electrode electrolyte is 0.05-3 mol/L, preferably 1-3 mol/L.
Preferably, the concentration of hydroxide ions in the positive electrode electrolyte is 0.1-5 mol/L.
Preferably, the positive electrolyte further comprises an auxiliary electrolyte, so that the electrolyte can form a uniform solvent, and the concentration of the auxiliary electrolyte in the positive electrolyte is 0.1-5 mol/L.
Preferably, the co-electrolyte is at least one of potassium chloride, sodium chloride, potassium sulfate or sodium sulfate.
The invention also provides application of the positive electrolyte in an alkaline zinc-iron flow battery.
Preferably, the alkaline zinc-iron flow battery is a flow battery which takes Fe (II)/Fe (III) as an active substance of a positive electrode electrolyte and Zn (II)/Zn as an active substance of a negative electrode electrolyte, and circulates and operates between a positive electrode and a diaphragm and between a negative electrode and the diaphragm through the positive electrode electrolyte and the negative electrode electrolyte respectively; wherein the positive and negative electrolytes have a pH of > 7.
Advantageous results of the invention
Crown ether substances or cavernous ligand compounds are added into the positive electrolyte, and alkali metal ions or alkaline earth metal ions are selectively complexed and coordinated, so that the concentration (activity) of cations in the positive electrolyte is reduced. In the alkaline zinc-iron flow battery, the actual active substance of the positive electrolyte is ferrous cyanide ions as anions, and corresponding cations of the positive electrolyte do not participate in battery reaction. Therefore, the concentration of cations is reduced by adding crown ether substances or cryptand compounds, so that the concentration of ferrous cyanide ions can be increased, the concentration of active substances in the electrolyte can be further increased, and the osmotic pressure of the positive electrode electrolyte is reduced. Therefore, the purposes of increasing the concentration of the active substance and reducing the osmotic pressure of the positive electrolyte can be realized. Furthermore, the concentration of the active substance is greatly increased, and the concentration of the conductive ions is improved, so that the charge and discharge capacity and the energy density of the battery are improved, and the battery performance of the alkaline zinc-iron flow battery is improved. Meanwhile, the osmotic pressure of the positive electrolyte is reduced, and the migration of the electrolyte is relieved, so that the long-time circulation stability of the alkaline zinc-iron flow battery is improved.
(1) The positive electrolyte can be prepared by adding crown ether substances or additives of cryptand compounds, so that the concentration of active substances, namely ferrocyanide is improved, and the osmotic pressure of the electrolyte is reduced.
(2) The positive electrolyte prepared by the invention has high active substance concentration, excellent electrolyte conductivity and stability and unobvious electrolyte migration, and greatly improves the charge-discharge capacity and the battery performance of the alkaline zinc-iron flow battery.
(3) The invention expands the variety and application range of the positive electrolyte for the zinc-iron flow energy storage battery in the alkaline system.
The preparation method of the anode electrolyte is simple, the process is environment-friendly, the concentration of active substances is high, and the osmotic pressure is low. Compared with the original anode electrolyte, the alkaline zinc-iron flow battery using the electrolyte as the anode has higher comprehensive performance.
Drawings
FIG. 1 is a schematic diagram of the molecular structure of 18-crown (ether) -6.
FIG. 2 is a schematic diagram of cryptand bound potassium ions (middle sphere).
FIG. 3 shows the results of example 1 and comparative example 1 at 80mA cm in an alkaline zinc-iron flow battery-2The charge and discharge performance at the current density of (c) was compared.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
422g of potassium ferrocyanide and 532g of 18-crown (ether) -6 are weighed, heated and stirred for 2h at 50 ℃, dissolved in 750mL of deionized water, and the solution is added to a constant volume of 1L, and the pH value of the solution is adjusted to 14 by potassium hydroxide. The concentration of the ferrocyanide in the obtained solution is 1mol/L, and the concentration of the 18-crown (ether) -6 is 2 mol/L.
The prepared electrolyte is utilized to assemble the alkaline zinc-iron flow battery, wherein the catalyst layer is an activated carbon felt, the bipolar plate is a graphite plate, the ion exchange membrane is a Nafion membrane produced by DuPont, and the effective area is 48cm2Current density of 80mA cm-2The concentration of zincate ions in the negative electrolyte is 0.5mol L-1The concentration of the ferrocyanide ions is 1mol L-1. The Coulombic Efficiency (CE) of the assembled alkaline zinc-iron flow battery was 98.8%, the Voltage Efficiency (VE) was 89.1%, and the Energy Efficiency (EE) was 88.0%. The average charge-discharge capacity of the battery is 1.12Ah, and the charge-discharge cycle life of the battery>2500 circles.
Comparative example 1
In comparison with example 1, the positive electrode electrolyte was changed to a saturated solution of potassium ferrocyanide (about 0.6mol/L) without adding 18-crown (ether) -6, and the other conditions were unchanged. The coulombic efficiency of the battery is 88.6%, the voltage efficiency is 83.3%, and the energy efficiency is 73.8%. The average charge-discharge capacity of the battery is 0.64Ah, and the charge-discharge cycle life of the battery is less than 500 circles.
Compared with a saturated potassium ferrocyanide solution, the alkaline ferrozinc flow battery using the positive electrolyte has the advantages that the coulombic efficiency, the energy efficiency, the charge-discharge capacity of the battery and the charge-discharge cycle life are obviously improved. The positive electrolyte prepared by adding the crown ether substance or the hole-shaped ligand compound effectively improves the concentration of active substances in the electrolyte, improves the conductivity of the battery electrolyte and reduces the osmotic pressure of the electrolyte, thereby improving the battery efficiency, the charge and discharge capacity and the battery cycle stability.
Example 2
In the same manner as in example 1, the positive electrode electrolyte was changed to sodium ferrocyanide and 18-crown (ether) -6, and the other conditions were not changed. The concentration of the ferrocyanide in the obtained solution is 2mol/L, and the concentration of the 18-crown (ether) -6 is 2 mol/L.
Example 3
In the same manner as in example 1, the positive electrode electrolyte was changed to lithium ferrocyanide and 12-crown-4, and the other conditions were not changed to obtain a solution in which the concentration of ferrocyanide was 1.5mol/L and the concentration of 12-crown-4 was 2 mol/L.

Claims (10)

1. An additive for positive electrolyte of an alkaline zinc-iron flow battery is characterized in that: the additive is at least one of a crown ether species comprising one or more of 15-crown (ether) -5, 18-crown (ether) -6, 12-crown (ether) -4, or dicyclohexyl-18-crown (ether) -6, or a cryptand compound comprising [2.2.2] -cryptand; the positive electrolyte of the alkaline zinc-iron flow battery is characterized in that cations in the positive electrolyte of the alkaline zinc-iron flow battery are one or more of sodium ions, potassium ions or lithium ions, and anions are divalent and/or trivalent iron cyanide complexes and hydroxide ions.
2. The positive electrode electrolyte for the alkaline zinc-iron flow battery is characterized in that: comprising the additive of claim 1; the molar concentration of the additive in the positive electrolyte is 0.01-2 mol/L.
3. The positive electrode electrolyte according to claim 2, characterized in that: the divalent and/or trivalent iron cyanide complex is ferricyanide (Fe (CN))6 3-) Or ferrocyanide (Fe (CN)6 4-) One or two of them.
4. The positive electrode electrolyte according to claim 2, characterized in that: the concentration of the divalent and/or trivalent iron cyanide complex in the positive electrode electrolyte is 0.05-3 mol/L.
5. The positive electrolyte as claimed in claim 4, wherein: the concentration of the divalent and/or trivalent iron cyanide complex in the positive electrode electrolyte is 1-3 mol/L.
6. The positive electrode electrolyte according to claim 2, characterized in that: in the positive electrode electrolyte, the concentration of hydroxide ions is 0.1-5 mol/L.
7. The positive electrode electrolyte according to claim 2, characterized in that: the positive electrolyte also comprises an auxiliary electrolyte, and the concentration of the auxiliary electrolyte in the positive electrolyte is 0.1-5 mol/L.
8. The positive electrolyte as claimed in claim 7, wherein: the auxiliary electrolyte is at least one of potassium chloride, sodium chloride, potassium sulfate or sodium sulfate.
9. Use of the anolyte of any of claims 2 to 8 in an alkaline zinc-iron flow battery.
10. Use according to claim 9, characterized in that: the alkaline zinc-iron flow battery is a flow battery which takes Fe (II)/Fe (III) as an active substance of a positive electrolyte and Zn (II)/Zn as an active substance of a negative electrolyte and circularly operates between a positive electrode and a diaphragm and between a negative electrode and the diaphragm through the positive electrolyte and the negative electrolyte respectively; wherein the positive and negative electrolytes have a pH of > 7.
CN201811458602.6A 2018-11-30 2018-11-30 Positive electrode electrolyte for alkaline zinc-iron flow battery and application Active CN111261910B (en)

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Citations (6)

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CN102731764A (en) * 2012-04-12 2012-10-17 中科院广州化学有限公司 Preparation method of double-metal cyanidation complex catalyst
CN102731765B (en) * 2012-04-12 2014-01-15 中科院广州化学有限公司 Preparation method of double-metal cyanidation complex catalyst
CN105247727A (en) * 2013-05-29 2016-01-13 日立汽车***株式会社 Lithium ion secondary battery
KR20180001967A (en) * 2016-06-28 2018-01-05 한국과학기술연구원 Crown ether-inclusive electrolyte for redox flow batteries and method of manufacturing the same
CN107834073A (en) * 2017-11-02 2018-03-23 南京航空航天大学 A kind of lithium metal battery negative pole dendrite inhibitor and its application method
CN108550910A (en) * 2018-04-16 2018-09-18 成都新柯力化工科技有限公司 A kind of nickelic ternary system lithium ion power battery electrolyte

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102731764A (en) * 2012-04-12 2012-10-17 中科院广州化学有限公司 Preparation method of double-metal cyanidation complex catalyst
CN102731765B (en) * 2012-04-12 2014-01-15 中科院广州化学有限公司 Preparation method of double-metal cyanidation complex catalyst
CN105247727A (en) * 2013-05-29 2016-01-13 日立汽车***株式会社 Lithium ion secondary battery
KR20180001967A (en) * 2016-06-28 2018-01-05 한국과학기술연구원 Crown ether-inclusive electrolyte for redox flow batteries and method of manufacturing the same
CN107834073A (en) * 2017-11-02 2018-03-23 南京航空航天大学 A kind of lithium metal battery negative pole dendrite inhibitor and its application method
CN108550910A (en) * 2018-04-16 2018-09-18 成都新柯力化工科技有限公司 A kind of nickelic ternary system lithium ion power battery electrolyte

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