CN111200146B - Negative electrode electrolyte for alkaline zinc-based flow battery and preparation and application thereof - Google Patents

Negative electrode electrolyte for alkaline zinc-based flow battery and preparation and application thereof Download PDF

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CN111200146B
CN111200146B CN201811372457.XA CN201811372457A CN111200146B CN 111200146 B CN111200146 B CN 111200146B CN 201811372457 A CN201811372457 A CN 201811372457A CN 111200146 B CN111200146 B CN 111200146B
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electrolyte
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袁治章
李先锋
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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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
    • H01M8/18—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 negative electrode electrolyte for an alkaline zinc-based flow battery, and preparation and application thereof, wherein the negative electrode electrolyte is a supermolecule complex solution formed by mixing a zinc precursor, an organic additive and strong base; the organic additive is micromolecular saccharide, micromolecular alcohol or a compound of the micromolecular saccharide and the micromolecular alcohol, is applied to the alkaline zinc-based flow battery, effectively inhibits the electrolyte migration of the alkaline zinc-based flow battery caused by inconsistent osmotic pressure of the positive electrolyte and the negative electrolyte, and greatly reduces the maintenance cost of the electrolyte in the actual use process of the battery.

Description

Negative electrode electrolyte for alkaline zinc-based flow battery and preparation and application thereof
Technical Field
The invention relates to the field of electrochemical energy storage of alkaline zinc-based flow batteries, in particular to a negative electrode electrolyte for an alkaline zinc-based 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 flexible system design, large storage capacity, free site selection, high energy conversion efficiency, 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, an emergency power supply system, a standby power station, an electric power system, peak clipping and valley filling and the like. The full-vanadium redox flow battery (VFB) is considered to have a good application prospect due to the advantages of high safety, good stability, high efficiency, long service life (the service life is more than 15 years), low cost and the like, but the electrolyte of the VFB is expensive, so that the large-scale application of the VFB is limited to a certain extent. The alkaline zinc-based flow battery is a novel flow battery with low cost and high open-circuit voltage, and has good prospect in large-scale application at present.
For example, the positive electrolyte of the existing alkaline zinc-iron flow battery adopts an alkaline solution of ferrocyanide, the negative electrolyte adopts a solution obtained by dissolving zinc salt or zinc oxide in strong alkali, and the battery of the electrolyte system has serious electrolyte migration due to irreversible water migration caused by ion migration due to inconsistent osmotic pressures of positive and negative electrolytes in the operation process, so that the voltage efficiency of the battery is reduced, the energy efficiency of the battery is further reduced, and the maintenance cost of the battery is greatly increased. Meanwhile, zinc deposition and dissolution are generated on the negative electrode side in the charging and discharging processes of the alkaline zinc-iron flow battery, serious zinc dendritic crystals or dendritic-like deposits are generated when the alkaline zinc-iron flow battery operates under the condition of high current density, and the continuously-grown dendritic crystals pierce a diaphragm to cause short circuit of the battery.
Disclosure of Invention
In order to solve the technical problems, it is particularly important to develop an alkaline zinc-based flow energy storage battery with low cost, simple structure and excellent performance, and in order to achieve the purposes, the specific technical scheme is as follows:
the invention provides a negative electrode electrolyte for an alkaline zinc-based flow battery, which is a supermolecule complex solution formed by mixing a zinc precursor, an organic additive and strong base; the organic additive is micromolecular saccharide, micromolecular alcohol or a compound of the micromolecular saccharide: glucose, fructose, lactose, maltose, sucrose; the small molecular alcohols are: mannitol, sorbitol, xylitol, glycerol, pentaerythritol, ethylene glycol; when the additive is a compound of the small molecular saccharides and the small molecular alcohols, the mass ratio of the small molecular saccharides to the small molecular alcohols is 1: 99-99: 1.
the zinc precursor is zinc salt or/and zinc oxide; zn (OH) generated after the zinc precursor is dissolved in strong alkali4 2-The molar concentration of (a) is 0.0001-2 mol/L; the molar concentration of the organic additive is 0.0001-1.5 mol/L; the molar concentration of the strong alkali is 0.0001-5 mol/L.
The battery comprises a battery module formed by connecting one or two or more single batteries in series/parallel, a liquid storage tank filled with positive and negative electrolyte, a circulating pump and a circulating pipeline, wherein the single batteries comprise a positive current collecting plate, a negative current collecting plate, a positive electrode, a negative electrode and an ion conducting membrane. The electrode is carbon felt or carbon paper;
the positive electrode of the alkaline zinc-iron flow battery adopts a mixed aqueous solution of ferrocyanide and strong base; the concentration of ferrocyanide in the positive electrolyte is 0.0001-1 mol/L, preferably 0.1-0.8 mol/L; the concentration of the strong alkali is 0.0001-5 mol/L;
the ferrocyanide comprises one or more of potassium ferrocyanide, sodium ferrocyanide, lithium ferrocyanide, magnesium ferrocyanide or calcium ferrocyanide.
Based on the above technical solution, preferably, the negative electrolyte further includes an auxiliary electrolyte; the auxiliary electrolyte is soluble salt; the auxiliary electrolyte is at least one of potassium chloride, sodium sulfate, sodium chloride, ammonium acetate and potassium sulfate so as to improve the conductivity of the electrolyte; the concentration of the auxiliary electrolyte is 0.001-5 mol/L.
Based on the technical scheme, preferably, the zinc precursor is at least one of zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, zinc carbonate and zinc oxide.
Based on the technical scheme, preferably, the strong base is at least one of sodium hydroxide, lithium hydroxide or potassium hydroxide.
Based on the above technical scheme, preferably, zn (oh) generated after the zinc precursor in the negative electrode solution is dissolved in strong alkali4 2-The concentration of (A) is 0.05-0.8 mol/L; the concentration of the strong base is 1-4 mol/L; the concentration of the organic additive is 0.1-1 mol/L.
Based on the technical scheme, it is further preferable that the molar concentration of the auxiliary electrolyte is 0.5-3 mol/L.
In another aspect of the present invention, a preparation method of the above negative electrode electrolyte is provided, wherein the electrolyte of the alkaline zinc-iron flow battery is prepared according to the following processes:
anode electrolyte: mixing ferrocyanide with strong base, dissolving in deionized water, and fully stirring at 20-100 ℃ for 0.5-10 hours to prepare a uniform solution as a positive electrolyte.
Negative electrode solution: (1) mixing zinc precursor with strong base, slowly adding deionized water, stirring to obtain uniform solution a, (2) adding organic additive into the above-mentioned solution a, slowly adding deionized water, stirring to form uniform solutionThe liquid is a negative electrode electrolyte. Based on the technical scheme, the preferable zinc precursor on the negative electrode side is dissolved in strong alkali to generate Zn (OH)4 2-And then the supermolecular complex formed with the organic additive generates electrochemical reaction of deposition and dissolution on the electrode, and the reaction equation is as follows:
Figure BDA0001869384580000031
the ferrocyanide or/and ferricyanide on the positive electrode side generates a valence change reaction of iron on the electrode, and the reaction equation is as follows:
Figure BDA0001869384580000032
during charging, the zinc precursor and the organic additive are dissolved in strong alkali to generate Zn (OH)4(CxHyOz)2-Then two electrons obtained on the carbon felt or carbon paper electrode are reduced into a simple substance of zinc; corresponding to the positive side, Fe (CN)6 4-Oxidation to Fe (CN) on carbon felt or carbon paper electrodes losing electrons6 3-。
In this case, Zn (OH) is formed on the negative electrode side4(CxHyOz)2-Electrochemical activity of supramolecular complexes with Zn (OH)4 2-Similarly, this is because the organic additive binds Zn (OH) by weaker secondary coordination4 2-Supramolecular complexes are formed and therefore the additive has less impact on battery performance. The content of oxygen on the supramolecular complex is obviously increased, including OH-And oxygen atoms on the organic matter, the oxygen atoms can form hydrogen bonds with hydrogen atoms of water molecules, and simultaneously oxygen atoms in the water can also form hydrogen bonds with hydrogen atoms on the supramolecular complex, so that the interaction between the supramolecular complex and the water is greatly enhanced, and the migration of the water molecules in the cathode electrolyte to the anode is inhibited. Meanwhile, the organic matter additive which does not participate in coordination increases the osmotic pressure of the negative electrolyte, and can also inhibit the negative electrodeThe water molecules in the electrolyte migrate to the positive electrode.
In the monocell or electric pile structure, the positive and negative electrolyte tanks are connected via liquid conveying pump to the positive and negative inlets and outlets of monocell or electric pile. When a single cell or a pile is charged, the electrolyte is respectively conveyed to the anode and the cathode from the anode and cathode liquid storage tanks by a pump, and the active substance Fe (CN) in the anode liquid storage tank6 4-Electrochemical oxidation reaction takes place to produce Fe (CN)6 3-，Zn(OH)4(CxHyOz)2-Ions are directly deposited on the carbon felt or carbon paper negative electrode in a simple substance form of zinc; when discharging, the zinc simple substance of the negative electrode is oxidized into Zn (OH) in the alkaline solution environment4(CxHyOz)2-The ions are pumped back to the negative electrode liquid storage tank, and the active material Fe (CN) in the positive electrode electrolyte corresponding to the ions6 3-Electrochemical reduction takes place to form Fe (CN)6 4-And then returns to the anode liquid storage tank through the pump.
The electrochemical oxidation-reduction potential generated by the negative electrode is different with the difference of the alkali concentration in the electrolyte, and the electrochemical oxidation-reduction potential range is between-0.74V vs.
Advantageous effects
(1) The problem of electrolyte migration of the alkaline zinc-based flow battery is effectively reduced: the organic additive effectively solves the problems of the traditional alkaline zinc-based flow battery that the electrolyte is transferred from one electrode to the other electrode and the efficiency of the battery is attenuated due to inconsistent osmotic pressures of the electrolytes of the positive electrode and the negative electrode in the operation process, and simultaneously effectively reduces the system maintenance cost caused by the electrolyte transfer, thereby showing good application prospect.
(2) The added organic additives have small influence on the performance of the battery: organic additives with Zn (OH) by weaker secondary complexation4 2-Formation of supramolecular complexes, formation of Zn (OH)4(CxHyOz)2-Electrochemical activity of supramolecular complexes with Zn (OH)4 2-Similarly, the battery can still maintain high performance while operating.
(3) Has higher energy density and power density: organic additive and Zn (OH) added into the negative electrode4 2-The supermolecule complex is formed, and the solubility of the negative active material is not influenced. The alkaline zinc-based flow battery with the negative electrode added with the organic matter additive can still show higher energy density and power density.
(4) The added organic additive has low cost: the listed organic additives have wide sources and are easy to purchase in the market, can keep the advantage of low cost of the alkaline zinc-iron flow battery, and have good application prospects in the field of energy storage.
(5) The added organic additive is safe and nontoxic: the listed organic additives are safe and non-toxic, so that the high safety and the high stability of the alkaline zinc-iron flow battery are ensured.
Drawings
Fig. 1 is a schematic structural diagram of an alkaline zinc-iron flow battery of the present invention.
Fig. 2 is a graph showing electrolyte migration tests of alkaline zinc-iron flow batteries in comparative examples and examples 1-4 of the present invention.
Fig. 3 is a graph of the efficiency of an alkaline zinc-iron flow cell of a comparative example.
Fig. 4 is a graph of the capacity of an alkaline zinc-iron flow battery of a comparative example.
Fig. 5 is a graph of the cycle performance of the alkaline zinc-iron flow battery of example 2.
Fig. 6 is a graph of the capacity of the alkaline zinc-iron flow battery of example 2.
Detailed Description
Comparative example
Alkaline zinc-iron flow battery test conditions without organic additives: electrode effective area: 48cm2(ii) a The battery adopts a constant current charging and discharging mode and is at 80mA cm-2Under the condition of current density of (1), charging for 18min, and then cutting off the voltage to 80mA cm-2Discharging to 0.1V under the current density condition of (1); positive electrode electrolyte composition: 0.8mol L-1Fe(CN)6 4-+3mol L- 1KOH; negative electrode electrolyte composition: 0.4mol L-1Zn(OH)4 2-+3mol L-1KOH; the volumes of the positive electrolyte and the negative electrolyte are respectively 80 mL; the positive electrode and the negative electrode are both porous carbon felt electrodes, and the graphite plate is used as a current collecting plate; the ion conducting membrane is a polybenzimidazole ion conducting membrane. Compared with the electrolyte composition of the traditional alkaline zinc-iron flow battery, the electrolyte composition of the positive electrode is 0.8mol L-1Fe(CN)6 4-+3mol L-1KOH; the composition of the cathode electrolyte is 0.4mol L-1Zn(OH)4 2-+3mol L-1KOH; the volumes of the positive electrolyte and the negative electrolyte are respectively 80 mL; the positive electrode and the negative electrode are both porous carbon felt electrodes, and the graphite plate is used as a current collecting plate; the ion conducting membrane is a polybenzimidazole ion conducting membrane; at 80mA cm-2Under the condition of current density of (1), charging for 18min, and then cutting off the voltage to 80mA cm-2Is discharged to 0.1V under the current density condition of (1). Measuring the volumes of the positive and negative electrolytes in the final stage of discharge, and as can be seen from the blank sample curve in fig. 2, in the conventional alkaline zinc-iron flow battery, the electrolytes migrate from the negative electrode to the positive electrode due to the unbalanced osmotic pressure of the positive and negative electrolytes in less than 50 circulation processes; the corresponding cell showed better cell performance in the first 100 cycles, but the cell efficiency (fig. 3) and the cell capacity (fig. 4) were greatly reduced in the latter period. Such a reduction in cell efficiency due to electrolyte migration will increase the maintenance cost of the system in practical applications, and is not suitable for large-scale applications.
Examples 1 to 5
The same test conditions for alkaline zinc-iron flow batteries in examples 1-5: electrode effective area: 48cm2(ii) a The battery adopts a constant current charging and discharging mode and is at 80mA cm-2Under the condition of current density of (1), charging for 18min, and then cutting off the voltage to 80mA cm-2Discharging to 0.1V under the current density condition of (1); positive electrode electrolyte composition: 0.8mol L-1Fe(CN)6 4-+3mol L-1KOH; the volumes of the positive electrolyte and the negative electrolyte are respectively 100 mL; the positive electrode and the negative electrode are both porous carbon felt electrodes, and the graphite plate is used as a current collecting plate; the ion conducting membrane is a polybenzimidazole ion conducting membrane. Except that the composition of the negative electrode electrolyte is as follows:
examples Negative electrode electrolyte composition
Example 1 0.4mol L-1Zn(OH)4 2-+3mol L-1KOH+0.3mol L-1Glucose
Example 2 0.4mol L-1Zn(OH)4 2-+3mol L-1KOH+0.5mol L-1Glucose
Example 3 0.4mol L-1Zn(OH)4 2-+3mol L-1KOH+0.5mol L-1Sorbitol
Example 4 0.4mol L-1Zn(OH)4 2-+3mol L-1KOH+0.5mol L-1Mannitol
Example 5 0.4mol L-1Zn(OH)4 2-+3mol L-1KOH+0.5mol L-1Xylitol, its preparation method and use
Assembling single cells: the cells were assembled in the following order: positive electrode end plate, graphite current collector and positive electrode 6x8cm2Carbon felt, polybenzimidazole ion conduction membrane and negative electrode 6x8cm2Carbon felt, graphite current collector, negative pole end plate. The cell structure is shown in figure 1.
Example 1
For the alkaline zinc-iron flow battery added with the organic additive, the composition of the positive electrolyte is 0.8mol L-1Fe(CN)6 4-+3mol L-1KOH; the composition of the cathode electrolyte is 0.4mol L-1Zn(OH)4 2-+3mol L-1KOH+0.3mol L-1Glucose; the volumes of the positive electrolyte and the negative electrolyte are respectively 80 mL; the positive electrode and the negative electrode are both porous carbon felt electrodes, and the graphite plate is used as a current collecting plate; the ion conducting membrane is a polybenzimidazole ion conducting membrane; at 80mA cm-2Under the condition of current density of (1), charging for 18min, and then cutting off the voltage to 80mA cm-2Is discharged to 0.1V under the current density condition of (1). And measuring the volume of the anode electrolyte and the cathode electrolyte at the final stage of discharge, wherein after 402 cycles, the volume of the cathode electrolyte is 90mL, the volume of the anode electrolyte is 70mL, the migration volume of the electrolyte is small, and meanwhile, the battery efficiency is not obviously attenuated after 635-time charge and discharge cycle investigation.
Example 2
For the alkaline zinc-iron flow battery added with the organic additive, the composition of the positive electrolyte is 0.8mol L-1Fe(CN)6 4-+3mol L-1KOH; the composition of the cathode electrolyte is 0.4mol L-1Zn(OH)4 2-+3mol L-1KOH+0.5mol L-1Glucose; the volumes of the positive electrolyte and the negative electrolyte are respectively 80 mL; the positive electrode and the negative electrode are both porous carbon felt electrodes, and the graphite plate is used as a current collecting plate; the ion conducting membrane is a polybenzimidazole ion conducting membrane; at 80mA cm-2Under the condition of current density of (1), charging for 18min, and then cutting off the voltage to 80mA cm-2Is discharged to 0.1V under the current density condition of (1). And measuring the volumes of the positive and negative electrolytes in the final stage of discharging, as shown in fig. 2, wherein a blank sample is the redox flow battery without the additive, and the volumes of the positive and negative electrolytes of the alkaline zinc-iron redox flow battery with the additive added in the negative electrolyte are not obviously changed within 600 cycles. The corresponding battery continuously and stably runs for 1200 cycles, the battery efficiency (figure 5) and the battery capacity (figure 6) are not obviously attenuated, excellent cycle stability is shown, and the problem that the electrolyte of the traditional alkaline zinc-iron flow battery is inconsistent in osmotic pressure of positive electrolyte solution and negative electrolyte solution is effectively solvedThe problems of migration and battery efficiency attenuation have more prospect in practical application.
Example 3
For the alkaline zinc-iron flow battery added with the organic additive, the composition of the positive electrolyte is 0.8mol L-1Fe(CN)6 4-+3mol L-1KOH; the composition of the cathode electrolyte is 0.4mol L-1Zn(OH)4 2-+3mol L-1KOH+0.5mol L-1Sorbitol; the volumes of the positive electrolyte and the negative electrolyte are respectively 80 mL; the positive electrode and the negative electrode are both porous carbon felt electrodes, and the graphite plate is used as a current collecting plate; the ion conducting membrane is a polybenzimidazole ion conducting membrane; at 80mA cm-2Under the condition of current density of (1), charging for 18min, and then cutting off the voltage to 80mA cm-2Is discharged to 0.1V under the current density condition of (1). And measuring the volumes of the anode electrolyte and the cathode electrolyte at the final stage of discharge, wherein after 375 cycles, the volume of the anode electrolyte is 89mL, the volume of the cathode electrolyte is 71mL, the migration volume of the electrolyte is small, and meanwhile, the battery efficiency is not obviously attenuated after 531 charge-discharge cycle examinations.
Example 4
For the alkaline zinc-iron flow battery added with the organic additive, the composition of the positive electrolyte is 0.8mol L-1Fe(CN)6 4-+3mol L-1KOH; the composition of the cathode electrolyte is 0.4mol L-1Zn(OH)4 2-+3mol L-1KOH+0.5mol L-1Mannitol; the volumes of the positive electrolyte and the negative electrolyte are respectively 80 mL; the positive electrode and the negative electrode are both porous carbon felt electrodes, and the graphite plate is used as a current collecting plate; the ion conducting membrane is a polybenzimidazole ion conducting membrane; at 80mA cm-2Under the condition of current density of (1), charging for 18min, and then cutting off the voltage to 80mA cm-2Is discharged to 0.1V under the current density condition of (1). And measuring the volumes of the anode electrolyte and the cathode electrolyte at the final stage of discharge, wherein after 409 cycles, the volume of the anode electrolyte is 87mL, the volume of the cathode electrolyte is 73mL, the migration amount of the electrolyte is small, and meanwhile, the battery efficiency is not obviously attenuated after 668 cycles of charge and discharge cyclic investigation.
Example 5
And for alkaline zinc-iron flow batteries with organic additives,the composition of the positive electrode electrolyte is 0.8mol L-1Fe(CN)6 4-+3mol L-1KOH; the composition of the cathode electrolyte is 0.4mol L-1Zn(OH)4 2-+3mol L-1KOH+0.5mol L-1Xylitol; the volumes of the positive electrolyte and the negative electrolyte are respectively 80 mL; the positive electrode and the negative electrode are both porous carbon felt electrodes, and the graphite plate is used as a current collecting plate; the ion conducting membrane is a polybenzimidazole ion conducting membrane; at 80mA cm-2Under the condition of current density of (1), charging for 18min, and then cutting off the voltage to 80mA cm-2Is discharged to 0.1V under the current density condition of (1). And measuring the volumes of the anode electrolyte and the cathode electrolyte at the final stage of discharge, wherein after 388 cycles, the volume of the anode electrolyte is 91mL, the volume of the cathode electrolyte is 69mL, the migration volume of the electrolyte is small, and meanwhile, the battery efficiency is not obviously attenuated after 525 times of charge-discharge cycle investigation.

Claims (9)

1. A negative electrode electrolyte for an alkaline zinc-based flow battery is characterized in that: the negative electrode electrolyte is a supermolecule complex solution formed by mixing a zinc precursor, an organic additive and strong base; the organic additive is micromolecular sugar, micromolecular alcohol or a compound of the micromolecular sugar and the micromolecular alcohol, and the micromolecular sugar is one or more than two of glucose, fructose, lactose, maltose or sucrose; the micromolecular alcohol is one or more than two of mannitol, sorbitol, xylitol, glycerol, pentaerythritol or glycol; when the organic additive is a compound of micromolecular sugar and micromolecular alcohol, the mass ratio of the micromolecular sugar to the micromolecular alcohol is 1: 99-99: 1.
2. the negative electrode electrolyte of claim 1, wherein Zn (OH) is formed after the zinc precursor is dissolved in a strong base4 2-The molar concentration of (a) is 0.0001-2 mol/L; the molar concentration of the organic additive is 0.0001-1.5 mol/L; the molar concentration of the strong alkali is 0.0001-5 mol/L.
3. The negative electrolyte of claim 1, wherein the negative electrolyte further comprises an auxiliary electrolyte; the auxiliary electrolyte is at least one of potassium chloride, sodium sulfate, sodium chloride, ammonium acetate and potassium sulfate; the molar concentration of the auxiliary electrolyte is 0.001-5 mol/L.
4. The negative electrode electrolyte of claim 1, wherein the zinc precursor is at least one of zinc chloride, zinc bromide, zinc iodide, zinc sulfate, zinc nitrate, zinc carbonate, and zinc oxide.
5. The negative electrode electrolyte of claim 1, wherein the strong base is at least one of sodium hydroxide, lithium hydroxide, or potassium hydroxide.
6. The negative electrode electrolyte as claimed in claim 2, wherein: the Zn (OH)4 2-The molar concentration of the organic additive is 0.05-0.8 mol/L, the molar concentration of the organic additive is 0.1-1 mol/L, and the molar concentration of the strong base is 1-4 mol/L.
7. The negative electrode electrolyte as claimed in claim 3, wherein the molar concentration of the auxiliary electrolyte is 0.5 to 3 mol/L.
8. The method for preparing the negative electrode electrolyte of claim 1, comprising the steps of: (1) mixing a zinc precursor and a strong base, adding deionized water, fully stirring for 0.5-10 hours at 20-100 ℃ to prepare a solution a, and (2) adding an organic additive into the solution a, adding deionized water, and fully stirring for 0.5-10 hours at 20-100 ℃ to prepare the cathode electrolyte.
9. Use of the negative electrolyte of claim 1 in an alkaline zinc-based flow battery, including an alkaline zinc-iron flow battery.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101677136A (en) * 2008-09-18 2010-03-24 中国人民解放军63971部队 Electrolyte solution for alkaline zinc flow battery
CN108461784A (en) * 2016-12-10 2018-08-28 中国科学院大连化学物理研究所 A kind of Alkaline Zinc iron liquid galvanic battery
WO2018201239A1 (en) * 2017-05-01 2018-11-08 Salient Energy Inc. Electrolyte additives for zinc metal electrodes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101677136A (en) * 2008-09-18 2010-03-24 中国人民解放军63971部队 Electrolyte solution for alkaline zinc flow battery
CN108461784A (en) * 2016-12-10 2018-08-28 中国科学院大连化学物理研究所 A kind of Alkaline Zinc iron liquid galvanic battery
WO2018201239A1 (en) * 2017-05-01 2018-11-08 Salient Energy Inc. Electrolyte additives for zinc metal electrodes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Zinc dendrites Inhibition for Zinc-based Battery;Wenjing Lu等;《ChemSusChem》;20180922;第11卷(第23期);第3996-4006页 *

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