CN115000480A - High-energy-density alkaline iron-sulfur flow battery and preparation method thereof - Google Patents

High-energy-density alkaline iron-sulfur flow battery and preparation method thereof Download PDF

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CN115000480A
CN115000480A CN202210897479.8A CN202210897479A CN115000480A CN 115000480 A CN115000480 A CN 115000480A CN 202210897479 A CN202210897479 A CN 202210897479A CN 115000480 A CN115000480 A CN 115000480A
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membrane
positive
flow battery
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electrolyte
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贾传坤
邹海涛
丁美
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Changsha University of Science and Technology
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Changsha University of Science and Technology
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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
    • 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 discloses a high-energy-density alkaline iron-sulfur flow battery and a preparation method thereof, wherein an active substance in a positive electrode electrolyte of the flow battery is ferricyanide or ferricyanide ions, and the concentration of the active substance on the positive electrode side is 0.1-1.7M; the active substance in the negative electrode electrolyte is one of sulfide solution or sulfur-containing organic compound, and the concentration range of the negative electrode active substance is 0.1-15M; the positive and negative electrolyte contains supporting electrolyte; the diaphragm is any one of a porous membrane, a ceramic membrane or an ion exchange membrane subjected to ionization treatment; the adjusting ions in the positive and negative electrolyte are the same as the positive ions of the negative active material and the supporting electrolyte. The method improves the solubility of ferricyanide/ferrocyanide, has the advantages of high energy density, long cycle life, low chemical cost, stable efficiency and the like, successfully inhibits the shuttle effect of polysulfide, and greatly reduces the installation cost of the flow battery.

Description

High-energy-density alkaline iron-sulfur flow battery and preparation method thereof
Technical Field
The invention belongs to the technical field of flow batteries, and relates to a high-energy-density alkaline iron-sulfur flow battery and a preparation method thereof.
Background
As the overuse of fossil energy brings problems such as energy shortage, environmental pollution and the like, secondary clean energy such as wind energy, solar energy and the like is used on a large scale. However, due to the inherent unstable and discontinuous characteristics of wind energy and photovoltaic power generation, further popularization and use are limited, and therefore, the development of a large-scale energy storage technology with high energy storage efficiency, low installation cost and stable circulation becomes a key point for popularization and use of renewable energy sources. Compared with the existing electrochemical energy storage technologies such as lithium ion batteries and lead-acid batteries, the all-vanadium redox flow battery has the advantages of capacity and power decoupling, long cycle life and high safety, and is one of the long-term high-efficiency energy storage technologies which are expected to be widely deployed. However, the existing all-vanadium redox flow battery with higher commercial maturity uses noble metal vanadium as electrolyte, and the diaphragm material is heavily dependent on import, so that the installation cost of the battery is too high, and meanwhile, the energy storage capacity of the vanadium redox flow battery is always limited by lower energy density. Therefore, it is necessary to develop a new flow battery system.
Ferricyanide/ferrocyanide has been widely used in various flow battery systems due to its advantages of abundant reserves, good stability, high electrochemical reversibility, low chemical cost, etc. Polysulfide is an ideal active material due to its high solubility and low cost. Flow batteries constructed using ferricyanide/ferrocyanide and polysulfides have shown excellent promise, with potential for gradual commercialization in the future. However, the low solubility of the ferricyanide/ferrocyanide on the positive electrode side makes the energy density of the battery too low (the solubility of sodium ferrocyanide and potassium ferrocyanide in pure water is only 0.56M and 0.76M), and this physicochemical property makes it difficult to realize high energy density design for the iron-sulfur flow battery system, and furthermore, the polysulfide on the negative electrode side has the problems of strong shuttle effect and low reactivity. Therefore, the invention adjusts the type, quantity and proportion of the anode and cathode supporting electrolytes, and successfully constructs the alkaline flow battery system with high energy density, good circulation stability and low chemical cost by using the high-performance diaphragm and the high-catalytic-activity electrode material.
Disclosure of Invention
In order to solve the problems, the invention provides a high-energy-density alkaline iron-sulfur flow battery, which improves the solubility of ferricyanide/ferrocyanide, has the advantages of high energy density, long cycle life, low chemical cost, stable efficiency and the like, successfully inhibits the shuttle effect of polysulfide, greatly reduces the installation cost of the flow battery, and has great practical significance for guiding the development of the high-energy-density flow battery.
Another object of the present invention is to provide a method for manufacturing a high energy density alkaline iron-sulfur flow battery.
The invention adopts the technical scheme that the high-energy-density alkaline iron-sulfur flow battery comprises a positive electrolyte, a negative electrolyte, a diaphragm, a positive electrode and a negative electrode, wherein an active substance in the positive electrolyte is ferricyanide or ferricyanide ions, and the concentration of the active substance on the positive electrode side is 0.1-1.7M;
the active substance in the negative electrode electrolyte is a sulfide solution, and the concentration range of the negative electrode active substance is 0.1-15M;
the supporting electrolyte in the positive and negative electrolytes is LiOH, NaOH, KOH or NH with the molar concentration of 0.1-6M 3 ·H 2 O、NH 4 HCO 3 、(NH 4 ) 2 CO 3、 Li 2 CO 3 、LiHCO 3 、Na 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 、Li 2 O、Na 2 O or K 2 One or more of O; when there are several kinds of supporting electrolytes for both the positive and negative electrodes, it is necessary to ensure that the supporting electrolytes for both the positive and negative electrodes have a common cation;
the diaphragm is any one of a porous membrane, a ceramic membrane or an ion exchange membrane subjected to ionization treatment;
the concentration range of the regulating ions in the positive and negative electrolytes is 0.1-2.0M, and the regulating ions are the same as the positive ions of the negative active substance and the supporting electrolyte.
Further, the positive and negative electrodes are carbon cloth, carbon paper, carbon felt, graphite plate, graphene modified carbon felt, graphite alkyne modified carbon felt, nickel net, modified nickel net and CuS 2 Modified electrode, CuS modified electrode, MoS 2 Modified electrode, CoS 2 Modified electrode, CoS modified electrode, NiS modified electrode, PbS modified electrode, SnS 2 Modified electrode, VS 2 Modified electrode, WS 2 Modified electrodes or FeS 2 Any one of the modified electrodes.
Further, the membrane is a perfluorosulfonic acid membrane (Nafion membrane), a sulfonated polyether ether ketone membrane (SPEEK membrane), a sulfonated polyimide membrane (SPI membrane), a sulfonated polyfluoreneether ketone membrane (SPFEK membrane), a polyvinylidene fluoride membrane (PVDF membrane), a polyether sulfone membrane (PES membrane), a sulfonated polyaryletherketone membrane (SPPEK membrane), a polyaryletherketone membrane (PAEK membrane), a polysulfone fiber membrane (PSF membrane), a polyphthalazinone ether ketone membrane (PPEKK membrane), a sulfonated polyether sulfone membrane (SPES membrane), a tetrafluoroethylene membrane (ETFE membrane), a polystyrene membrane (PS membrane), a polyethylene membrane (PE membrane), a polyphenyleneene membrane (PP membrane), a polybenzimidazole membrane (PBI membrane), a sulfonated polyaryletherketone membrane, a polyparaphenylene membrane, a sulfonated polydiallylbisphenol ether ketone membrane, a polyfluoreneether ketone sulfone membrane, a polyfluoreneether ether membrane, Any one of a polyvinyl chloride acylated membrane, a polyphenyl ether membrane or a polyphenyl membrane.
Further, the sulfide solution is one or more of potassium sulfide, potassium polysulfide, sodium sulfide, sodium polysulfide, lithium sulfide, lithium polysulfide, calcium sulfide, calcium polysulfide, rubidium sulfide, cesium sulfide, aluminum sulfide, magnesium sulfide, zinc sulfide, benzenesulfonic acid, thiol, thiophenol or thioether which are mixed in any mass ratio.
Furthermore, when the number of the supporting electrolytes in the positive and negative electrolytes is two, the total molar concentration is 0.1-6M, and the molar ratio of the two supporting electrolytes is in the range of 1/6-6/1.
Further, when the number of the supporting electrolytes in the positive and negative electrolytes is three, the total molar concentration is 0.5-5.0M, and the molar ratio of the three supporting electrolytes is within the range of 1:1: 1-6: 3: 1.
Further, when the number of the supporting electrolytes in the positive and negative electrolytes is four, the total molar concentration is 0.5M-4.0M, and the molar ratio of the four supporting electrolytes is in the range of 1:1: 1-6: 1:1: 1.
A preparation method of a high-energy density alkaline iron-sulfur flow battery comprises the following steps:
preparing a diaphragm: the diaphragm is any one of an ion exchange membrane, a porous membrane or a ceramic membrane; when the diaphragm is an ion exchange membrane, carrying out ionization treatment;
preparing an electrode: carbon cloth, carbon paper, carbon felt, graphite plate, graphene modified carbon felt, graphite alkyne modified carbon felt, nickel net, modified nickel net and CuS 2 Modified electrode, CuS modified electrode, MoS 2 Modified electrode, CoS 2 Modified electrode, CoS modified electrode, NiS modified electrode, PbS modified electrode, SnS 2 Modified electrode, VS 2 Modified electrode, WS 2 Modified electrodes or FeS 2 The modified electrode is used as an electrode material of a battery;
preparing a negative electrode electrolyte: dissolving potassium sulfide, potassium polysulfide, sodium sulfide, sodium polysulfide, lithium sulfide, lithium polysulfide, calcium sulfide, calcium polysulfide, rubidium sulfide, cesium sulfide, aluminum sulfide, magnesium sulfide, zinc sulfide, benzenesulfonic acid, mercaptan, thiophenol or thioether in an alkaline solution to obtain an alkaline solution of sulfide; adding 0.1-2.0M of regulating ions, wherein the regulating ions are LiCl, KCl, NaCl, LiBr, KBr, NaBr, LiI, KI, NaI and Li 2 SO 4 、LiNO 3 、K 2 SO 4 、KNO 3 、Na 2 SO 4 、NaNO 3 、NH 4 Cl or (NH) 4 ) 2 SO 4 Any one or more of the solutions are mixed, and a magnetic stirrer is used for fully stirring and dissolving;
preparing a positive electrolyte: dissolving one or more of potassium ferricyanide, potassium ferrocyanide, sodium ferricyanide, ammonium ferrocyanide, lithium ferricyanide or lithium ferrocyanide in an alkaline solution to prepare an alkaline solution of ferricyanide/ferrocyanide; then adding 0.1-2.0M of regulating ions, wherein the regulating ions are LiCl, KCl, NaCl, LiBr, KBr, NaBr, LiI, KI, NaI and Li 2 SO 4 、LiNO 3 、K 2 SO 4 、KNO 3 、Na 2 SO 4 、NaNO 3 、NH 4 Cl or (NH) 4 ) 2 SO 4 Any one or more of the solutions are mixed, and a magnetic stirrer is used for fully stirring and dissolving;
and assembling the prepared positive and negative electrolytes, the diaphragm and the positive and negative electrodes into the alkaline redox flow battery.
Further, the alkaline solution in the preparation of the negative electrolyte and the preparation of the positive electrolyte is a supporting electrolyte, and the preparation method comprises the following steps: preparing LiOH, NaOH, KOH and NH by using deionized water 3 ·H 2 O、NH 4 HCO 3 、(NH 4 ) 2 CO 3、 Li 2 CO 3 、Li 2 HCO 3 、Na 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 、Li 2 O、Na 2 O or K 2 O, one or more alkali solutions with the total molar concentration of 0.1-6M; when there are several supporting electrolytes for both positive and negative electrodes, it is necessary to ensure that the supporting electrolytes for both positive and negative electrodes have a common cation.
Further, in the preparation of the diaphragm, the ionization treatment of the ion exchange membrane: passing through LiOH, NaOH, KOH and NH with the concentration of 0.1-6.0M 3 ·H 2 O、NH 4 HCO 3 、(NH 4 ) 2 CO 3 、Li 2 CO 3 、Li 2 HCO 3 、Na 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 、Li 2 O、Na 2 O or K 2 Carrying out constant-temperature heating treatment on the ion exchange membrane by any alkali solution in O at the heating temperature of 40-100 ℃ for 0.5-8 h, cleaning by using deionized water after the ionization process is finished, and soaking in the deionized water to obtain K + 、Na + 、Li + Or NH 4 + Forming an ion exchange membrane, and finally soaking the membrane in LiCl, KCl, NaCl, LiBr, KBr, NaBr, LiI, KI, NaI and Li with the concentration of 0.1-2.0M 2 SO 4 、LiNO 3 、K 2 SO 4 、KNO 3 、Na 2 SO 4 、NaNO 3 、NH 4 Cl、NH 4 Br or (NH) 4 ) 2 SO 4 The solution is ready for use.
The beneficial effects of the invention are:
1. according to the invention, the concentration of ferricyanide/ferrocyanide is successfully increased to 1.7M by regulating the type, the quantity and the proportion of the active substance on the positive electrode side and the supporting electrolyte, so that the solubility limit of ferricyanide/ferrocyanide is unlocked, and the ferricyanide/ferrocyanide can be completely dissolved at room temperature, and compared with the existing flow battery technology, the high energy density can be realized. When high-concentration ferricyanide/ferrocyanide is used on the positive electrode side, the battery can still maintain excellent cycling stability, and no phenomenon of crystal precipitation is found on the positive electrode side, which shows that the iron compound electrolyte designed by the system has excellent physicochemical properties.
2. On the basis of improving the concentration of the positive iron compound, the invention adjusts the type, quantity and proportion of the supporting electrolyte by constructing a strategy that the auxiliary ions are consistent with the positive ions of the active substance, successfully inhibits the shuttle effect of polysulfide and effectively prolongs the cycle service life of the battery. Meanwhile, the invention uses ferricyanide/ferrocyanide and polysulfide with low chemical cost as active substances, thereby effectively solving the problem of high chemical cost of the electrolyte, namely having the advantages of high energy density, low chemical cost and long cycle life.
3. In order to solve the problems of slow shuttle effect and reaction activity of polysulfide, a long-term stable circulating alkaline iron-sulfur flow battery system is constructed by using a high-performance diaphragm and an electrode material with high catalytic activity, and assistance can be provided for the development of the flow battery in the large-scale and energy storage field.
4. The embodiment of the invention has the advantages of abundant reserves of all active substances, low cost, environmental friendliness, no strong corrosive material, effective reduction of equipment investment cost and operation and maintenance cost, and contribution to realization of industrialization and scale of the technical scheme.
In a word, the invention greatly improves the solubility of ferricyanide/ferrocyanide and the stability of negative polysulfide in the circulation process by adjusting the type, quantity and proportion of the positive and negative supporting electrolytes, develops and uses a high-performance diaphragm material and a high-catalytic-activity electrode, realizes the design of the high-energy-density iron-sulfur flow battery with long-term stable circulation, and still has longer cycle life in a battery stack system.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a graph of the cycling performance of a flow battery in example 1 of the invention.
Fig. 2 is a graph of the cycling performance of a flow battery in example 2 of the invention.
Fig. 3 is a graph of the cycling performance of a flow battery in example 3 of the invention.
Fig. 4 is a graph of capacity voltage of the flow battery in example 3 of the invention.
Fig. 5 is a graph of rate performance of a flow battery in example 3 of the invention.
Fig. 6 is a graph of the cycling performance of the flow battery in example 4 of the invention.
Fig. 7 is a graph of the cycling performance of a flow battery in example 5 of the invention.
Fig. 8 is a graph of the cycling performance of the flow battery in example 6 of the invention.
Fig. 9 is a graph of the cycling performance of the flow battery in example 7 of the invention.
Fig. 10 is a graph of the cycling performance of the flow battery in example 8 of the invention.
Fig. 11 is a graph of the cycling performance of a flow battery in example 9 of the invention.
Fig. 12 is a graph of the cycling performance of a flow battery in example 10 of the invention.
Fig. 13 is a graph of the cycling performance of a flow battery in example 11 of the invention.
Fig. 14 is a graph of the cycling performance of a flow battery in example 12 of the invention.
Fig. 15 is a graph of the cycling performance of a flow battery in example 13 of the invention.
Fig. 16 is a graph of the cycling performance of a flow battery in example 14 of the invention.
Fig. 17 is a graph of the cycling performance of the flow battery in example 15 of the invention.
Fig. 18 is a graph of the cycling performance of a flow battery in example 16 of the invention.
FIG. 19 is a graph of cycle performance in comparative example 1 of the present invention.
FIG. 20 is a graph comparing the capacity and voltage of comparative example 4 and example 6 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The design idea of the invention is as follows:
ferricyanide/ferrocyanide as a low cost, chemically stable active material has been limited by low solubility, and has always been the place of the introduction of its development applications, even though polysulfides have good water solubility, it is difficult to achieve high volumetric capacity on both sides of the cell. The invention changes the actual solubility of ferricyanide/ferrocyanide by continuously adjusting the type, quantity and proportion of supporting electrolyte, and finally obtains the optimum concentration for improving ferricyanide/ferrocyanide. Meanwhile, in order to construct a polysulfide which is stable in long-term operation, the influence of the supporting electrolyte of the negative electrode on the polysulfide in the circulating process is further regulated and controlled, the type, the quantity and the proportion of the supporting electrolyte are screened, and the optimal supporting electrolyte concentration of the stable polysulfide is further obtained. Meanwhile, in order to construct a battery system with long-term stable circulation, different types of diaphragms and different electrode materials are further designed and screened, the height replacing effect on the battery performance is achieved, and finally a flow battery system with strong practical usability is developed.
A high-energy-density alkaline iron-sulfur flow battery system comprises a single battery or a galvanic pile consisting of two or more single batteries. Basic composition of the single cell: the external liquid storage tanks of the positive electrode and the negative electrode, the positive electrode half cell, the negative electrode half cell, the diaphragm and the corresponding transmission pipelines; the external liquid storage tanks of the positive and negative electrodes are used for storing positive and negative electrolyte, and the electrolyte is conveyed to the interior of the battery to complete reaction under the action of the pump during battery testing. The positive half cell consists of an electrode, a tab and a sealing material, and the negative half cell is similar to the positive half cell; the positive and negative half batteries are separated by a diaphragm.
The diaphragm is any one of an ion exchange membrane, a porous membrane or a ceramic membrane. The ion exchange membrane uses the principle that protons/ions are conducted by anions and cations, and active substances of positive and negative electrodes cannot penetrate through the membrane. The porous membrane and the ceramic membrane are membranes with larger pore diameters, and the shuttle effect of polysulfide cannot occur in the invention because a regulating ion strategy is added, and even if the membranes with larger pore diameters are used, the battery can still normally and stably run.
The ion exchange membrane is selected from perfluorosulfonic acid membrane (Nafion membrane), sulfonated polyether ether ketone membrane (SPEEK membrane), sulfonated polyimide membrane (SPI membrane), sulfonated polyfluorene ether ketone membrane (SPEK membrane), polyvinylidene fluoride membrane (PVDF membrane), polyether sulfone membrane (PES membrane), sulfonated polyaryletherketone membrane (SPPEK membrane), polyaryletherketone membrane (PAEK membrane), polysulfone fiber membrane (PSF membrane), polyphthalazinone ether ketone membrane (PPEKK membrane), sulfonated polyether sulfone membrane (SPES membrane), tetrafluoroethylene membrane (ETFE membrane), polystyrene membrane (PS membrane), polyethylene membrane (PE membrane), polyphenyleneene membrane (PP membrane), polybenzimidazole membrane (PBI membrane), sulfonated polyaryletherketone membrane, polyparaphenylene membrane, sulfonated polydiallylbisphenol ether ketone membrane, polyfluorene ether sulfone membrane, polyfluorene ether, polychloroethylene acylation membrane, Ion exchange membranes such as polyphenyl ether membranes or polyphenyl membranes, porous membranes, and ion exchange membranes in ceramic membranes.
Treatment of the ion exchange membrane: by LiOH, NaOH, KOH, NH 3 ·H 2 O、NH 4 HCO 3 、(NH 4 ) 2 CO 3 、Li 2 CO 3 、Li 2 HCO 3 、Na 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 、Li 2 O、Na 2 O or K 2 Carrying out constant-temperature heating treatment on the ion exchange membrane by any alkali solution in O at the heating temperature of 40-100 ℃ for 0.5-8 h, cleaning by using deionized water after the ionization process is finished, and soaking in the deionized water to obtain K + 、Na + 、Li + Or NH 4 + Forming ion exchange membrane, and soaking in LiCl, KCl, NaCl, LiBr, KBr, NaBr, LiI, KI, NaI, Li 2 SO 4 、LiNO 3 、K 2 SO 4 、KNO 3 、Na 2 SO 4 、NaNO 3 、NH 4 Cl、NH 4 Br or (NH) 4 ) 2 SO 4 The solution is ready for use. If the alkali solution is Li 2 O、Na 2 O or K 2 O, the prepared separators are respectively Li + 、Na + 、K + And (3) a diaphragm.
The porous membrane and the ceramic membrane do not need to be subjected to the above treatment, and can be directly used for the flow battery system of the embodiment of the invention.
The electrode is carbon cloth, carbon paper, carbon felt, graphite plate, graphene modified carbon felt, graphite alkyne modified carbon felt, nickel net, modified nickel net, CuS 2 Modified electrode, CuS modified electrode, MoS 2 Modified electrode, CoS 2 Modified electrode, CoS modified electrode, NiS modified electrode, PbS modified electrode, SnS 2 Modified electrode, VS 2 Modified electrode, WS 2 Modified electrodes or FeS 2 Any one of the modified electrodes. Electrode material (modified nickel screen, CuS) with high catalytic activity 2 Modified electrode, CuS modified electrode, MoS 2 Modified electrode, CoS 2 Modified electrode, CoS modified electrode, NiS modified electrode, PbS modified electrode, SnS 2 Modified electrode, VS 2 Modified electrode, WS 2 Modified electrodes or FeS 2 Modified electrode) enables rapid reaction of polysulfides, which can effectively increase energy efficiency and power density of the battery. The basic principle is based on carbon felt electrode materialThe prepared modified electrode effectively increases the conductivity of the electrode on one hand, and effectively loads sulfide on the original carbon felt on the other hand, so that the reactive active sites of polysulfide ions can be effectively increased, and the reaction rate of active substances is finally accelerated.
The positive electrode active material is ferricyanide or ferricyanide ions, in some embodiments, two or more of potassium ferricyanide, potassium ferrocyanide, sodium ferricyanide, ammonium ferrocyanide, lithium ferricyanide, or lithium ferrocyanide (molar ratio 1: mixed), the concentration of the configured iron compound is related to the type, ratio, and amount of the corresponding compound and supporting electrolyte, and the concentration of the configured positive electrode side active material is 0.1M to 1.7M.
The negative electrode active material is one of a sulfide solution or a sulfur-containing organic compound having extremely high water solubility.
The concentration range of the negative electrode active substance in the negative electrode electrolyte is 0.1-15M. Polysulfide is a substance with extremely high water solubility, and the concentration range set in the examples of the present invention is because polysulfide has inherent solubility in this range. In addition, higher concentrations of polysulfides cannot be used with conventional iron-sulfur flow batteries because the higher shuttling effect of polysulfides can reduce the cycle life of the battery, which effect is more severe when polysulfides are at higher concentrations.
The highest concentration of polysulfide used in a typical iron-sulfur flow battery is only 2.0M K 2 S, which means that the cell cannot build a bilateral high energy density cell system. The invention constructs a bilateral alkaline iron-sulfur flow battery system with high energy density, and has longer cycle life compared with the common iron-sulfur flow battery. On the one hand, ferricyanide/ferrocyanide with higher solubility was successfully developed in alkaline, and high volume capacity design was achieved on the positive side. On the other hand, an ion regulation strategy is designed, so that the shuttle effect of polysulfide is successfully reduced, and the cycle life of the battery is prolonged. In addition, a high-performance separator and a high-catalytic-activity electrode material are further used. High ion selectionThe porous membrane can further help to inhibit the shuttle effect of polysulfide, and the electrode material can improve the reactivity of polysulfide ions and the adsorption performance of the polysulfide ions and reduce the shuttle effect of the polysulfide ions. Therefore, the alkaline iron-sulfur flow battery of the invention has higher energy density, longer cycle life and lower chemical cost than the prior iron-sulfur flow battery.
The sulfide solution is one or more of potassium sulfide, potassium polysulfide, sodium sulfide, sodium polysulfide, lithium sulfide, lithium polysulfide, calcium sulfide, calcium polysulfide, rubidium sulfide, cesium sulfide, aluminum sulfide, magnesium sulfide, zinc sulfide, benzenesulfonic acid, mercaptan, thiophenol or thioether which are mixed in any mass ratio. The polysulfide ions S of varying valence are used in the actual reaction process X （X=1，2，3，4，5，6，7，8）。
The supporting electrolyte in the positive and negative electrolyte is LiOH, NaOH, KOH, NH 3 ·H 2 O、NH 4 HCO 3 、(NH 4 ) 2 CO 3、 Li 2 CO 3 、Li 2 HCO 3 、Na 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 、Li 2 O、Na 2 O or K 2 O, and the total molar concentration of one or more of O and O is 0.1-6M.
Li 2 O、Na 2 O or K 2 O is used as a supporting electrolyte, on one hand, an alkaline environment is provided, and the solubility of the ferricyanide/ferrocyanide at the positive electrode is ensured. On the other hand, the ionic conductivity of the solution is ensured, and corresponding ions can be stably conducted under the corresponding cationic ion exchange membrane.
When two supporting electrolytes are used for both the positive electrode and the negative electrode, the total molar concentration is 0.1M-6M, the molar ratio is in the range of 1/6-6/1, and particularly in the range of 1/2-6/1. When three supporting electrolytes are used for the positive electrode and the negative electrode, the sum of the total concentration is 0.5M to 5.0M, and the molar ratio is in the range of 1:1:1 to 6:3: 1. When four supporting electrolytes are used for the positive electrode and the negative electrode, the sum of the total concentration is 0.5M to 4.0M, and the molar ratio is in the range of 1:1:1 to 6:1:1: 1.
When the cation of the supporting electrolyte in the negative electrolyte is one, the cation is one of the cations of the supporting electrolyte in the positive electrolyte, that is, when there are several supporting electrolytes in the positive and negative electrodes, it is necessary to ensure that the supporting electrolytes have a common cation. When the positive and negative electrolytes or cations of the active material are not uniform during the cycling test of the battery. Due to the specific cation or anion exchange membrane, cations different from the diaphragm can be gradually blocked on the diaphragm, the polarization of the battery is increased, and the cycling stability of the battery is finally influenced.
The shuttling effect of polysulfide is an inherent problem, and the problem is more serious at high concentration, and how to solve the shuttling effect of polysulfide and further improve the cycle stability of an iron-sulfur flow battery system is a current technical problem. The present invention supports the consistency of the cations in the electrolyte, polysulfides and auxiliary ions for reducing the shuttling effect of polysulfides.
Polysulfide is very easily oxidized in the battery cycle process, and elemental sulfur precipitates can be generated to influence the performance of the battery. The embodiment of the invention uses potassium polysulfide, and the solution containing potassium ions has better performance on the battery. On one hand, the cations of the supporting electrolyte and the active material are kept consistent, so that the polarization of the battery in the circulating process can be reduced, and the service life of the battery can be prolonged. On the other hand, in order to construct a double-side high-energy-density iron-sulfur flow battery system, high-concentration potassium polysulfide is needed on the negative electrode side, but the shuttling effect of the high-concentration potassium polysulfide is strong, the cycle performance of the battery is influenced, and the potassium ion conductivity of the solution can be enhanced, the shuttling of polysulfide ions and the oxidation of the polysulfide ions can be reduced by adding a solution containing potassium ions as a supporting electrolyte.
A preparation method of a high energy density alkaline iron-sulfur flow battery system comprises the following steps:
(1) preparing LiOH, NaOH, KOH and NH by using deionized water 3 ·H 2 O、NH 4 HCO 3 、(NH 4 ) 2 CO 3、 Li 2 CO 3 、Li 2 HCO 3 、Na 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 、Ca(OH) 2 、Li 2 O、Na 2 O、K 2 O, one or more alkali solutions;
(2) using a perfluorosulfonic acid membrane (Nafion membrane), a sulfonated polyether ether ketone membrane (SPEEK membrane), a sulfonated polyimide membrane (SPI membrane), a sulfonated polyfluoreneether ketone membrane (SPFEK membrane), a polyvinylidene fluoride membrane (PVDF membrane), a polyether sulfone membrane (PES membrane), a sulfonated polyaryletherketone membrane (SPPEK membrane), a polyaryletherketone membrane (PAEK membrane), a polysulfone fiber membrane (PSF membrane), a polyphthalazinone ether ketone membrane (PPEKK membrane), a sulfonated polyether sulfone membrane (SPES membrane), a tetrafluoroethylene membrane (ETFE membrane), a polystyrene membrane (PS membrane), a polyethylene membrane (PE membrane), a polyphenylene membrane (PP membrane), a polybenzimidazole membrane (PBI membrane), a sulfonated polyaryletherketone membrane, a polyparaphenylene membrane, a sulfonated polydiallylbisphenol ether ketone membrane, a polyfluoreneether ketone sulfone membrane, a polyfluoreneether ether membrane, a polyvinyl chloride acylated membrane (pvc membrane), A polyphenylene ether diaphragm or a polyphenylene diaphragm or the like as a diaphragm;
(3) the diaphragm in step (2) comprises an ion exchange membrane, a porous membrane and a ceramic membrane, which illustrates the wide applicability of the system of the invention to diaphragms. Wherein, the ion exchange membrane is subjected to ionization treatment according to the following steps: carrying out constant-temperature heating treatment on the ion exchange membrane in the alkali solution (0.1-6.0M) in the step (1), wherein the heating time is 0.5-8 h at 40-100 ℃, the purpose of ionizing treatment is to improve the ionic conductivity of the membrane, and the membrane is converted into a specific ion exchange type membrane; the non-ion exchange membrane can be directly used in the flow battery of the system;
(4) repeatedly cleaning the specific ionic exchange membrane converted in the step (3) by using deionized water until the water solution finally soaking the membrane is neutral, and soaking the membrane in 0.1-2.0M LiCl, KCl, NaCl, LiBr, KBr, NaBr, LiI, KI, NaI and Li 2 SO 4 、LiNO 3 、K 2 SO 4 、KNO 3 、Na 2 SO 4 、NaNO 3 、NH 4 Cl or (NH) 4 ) 2 SO 4 The solution is ready for use;
(5) carbon cloth, carbon paper, carbon felt, graphite plate, graphene modified carbon felt, graphite alkyne modified carbon felt, nickel net, modified nickel net and CuS 2 Modified electrode, CuS modified electrode, MoS 2 Modified electrode, CoS 2 Modified electrode, CoS modified electrode, NiS modified electrode, PbS modified electrode, SnS 2 Modified electrode, VS 2 Modified electrode, WS 2 Modified electrodes or FeS 2 Modified electrodes and the like are used as electrode materials for batteries;
(6) dissolving sulfides such as potassium sulfide, potassium polysulfide, sodium sulfide, sodium polysulfide, lithium sulfide, lithium polysulfide, calcium sulfide, calcium polysulfide, rubidium sulfide, cesium sulfide, aluminum sulfide, magnesium sulfide, zinc sulfide, benzenesulfonic acid, mercaptan, thiophenol, thioether and the like and sulfur-containing organic compounds in the alkali solution prepared in the step (1) to obtain an alkali solution of sulfides;
(7) dissolving one or more of potassium ferricyanide, potassium ferrocyanide, sodium ferricyanide, ammonium ferrocyanide, lithium ferricyanide or lithium ferrocyanide in the alkaline solution prepared in the step (1) to prepare a ferricyanide/ferrocyanide alkaline solution;
(8) in order to construct the similar ion for regulating the circulation stability of the positive and negative electrode active materials, 0.1-2.0M of regulating ions are LiCl, KCl, NaCl, LiBr, KBr, NaBr, LiI, KI, NaI and Li on the basis of the solutions prepared in the step (6) and the step (7) 2 SO 4 、LiNO 3 、K 2 SO 4 、KNO 3 、Na 2 SO 4 、NaNO 3 、NH 4 Cl or (NH) 4 ) 2 SO 4 One or more of the solutions are fully stirred and dissolved by a magnetic stirrer and finally used as positive and negative electrolyte of the battery; the concentration of the additive, including the specific species, amount and corresponding ratio, is determined continuously by experiment. If it is out of the range, since the active material and the supporting electrolyte, and the above-mentioned materials added are water-soluble, a high volume capacity is requiredThe positive and negative electrode solutions of (1) can ensure that the concentration of the rest substances is not too high under the condition of ensuring higher active substance concentration, so that the concentration of the rest substances is not too high on the premise of ensuring volume capacity.
(9) The electrolytes prepared in steps (3), (4), (5), (6), (7) and (8) and key materials are assembled into an alkaline redox flow battery, and the alkaline redox flow battery is tested by using a battery test system such as novacar, blue battery, Arbin and the like.
In the case of the example 1, the following examples are given,
a high energy density alkaline iron-sulfur flow battery: k of positive active material of flow battery is 0.1mol/L 4 Fe(CN) 6 And 0.1mol/L of Na 4 Fe(CN) 6 The supporting electrolyte is 1.0mol/L KOH; k of 1.0mol/L as a negative electrode active material 2 S, 0.5mol/L KOH supporting electrolyte; the membrane adopts modified Nafion to conduct K + A diaphragm; carbon felts are used as the anode and cathode electrode materials. Wherein, the modified Nafion conducts K + Preparing a diaphragm: carrying out constant-temperature heating treatment on the ion exchange membrane by KOH with the concentration of 0.1M, wherein the heating temperature is 40 ℃, the heating time is 8h, and after the ionization process is finished, cleaning the ion exchange membrane by using deionized water and soaking the ion exchange membrane in the deionized water to obtain K + Forming an ion exchange membrane, and finally soaking in a KCl solution with the concentration of 0.1M for later use.
The alkaline iron-sulfur flow battery of example 1 was subjected to constant current charge-discharge cycling performance test, with the flow rates of the positive electrolyte and the negative electrolyte being 20mL/min, the charge cut-off voltage being 1.2V, the discharge cut-off voltage being 0.6V, and the current density being 20mA/cm 2 As shown in fig. 1, the average coulombic efficiency of the flow battery system in this example is 99.6%, the average voltage efficiency is 64.4%, and the average energy efficiency is 64.1%.
In the case of the example 2, the following examples are given,
a high energy density alkaline iron-sulfur flow battery: the positive active material of the flow battery adopts 0.1mol/L K 4 Fe(CN) 6 And 0.1mol/L of Na 4 Fe(CN) 6 The supporting electrolyte is 1.0mol/L KOH; k of 1.0mol/L as a negative electrode active material 2 S, KOH supporting electrolyte 0.5mol/L, and KCl 1.0mol/L asAdjusting positive and negative electrolytes for auxiliary ions; the membrane adopts modified Nafion to conduct K + A diaphragm; carbon felts are used as the anode and cathode electrode materials. Wherein, the modified Nafion conducts K + Preparing a diaphragm: carrying out constant-temperature heating treatment on the ion exchange membrane by KOH with the concentration of 6.0M, wherein the heating temperature is 60 ℃, the heating time is 3 hours, and after the ionization process is finished, cleaning the ion exchange membrane by using deionized water and soaking the ion exchange membrane in the deionized water to obtain K + Forming an ion exchange membrane, and finally soaking in a KCl solution with the concentration of 2.0M for later use.
The alkaline iron-sulfur flow battery of example 2 was subjected to constant current charge-discharge cycling performance test, with the flow rates of the positive electrolyte and the negative electrolyte being 20mL/min, the charge cut-off voltage being 1.2V, the discharge cut-off voltage being 0.6V, and the current density being 20mA/cm 2 As shown in fig. 5, the average coulombic efficiency of the flow battery system in this example was 98.8%, the average voltage efficiency was 82.5%, and the average energy efficiency was 83.5%. The cell efficiency using the conditioning ion under the same conditions is higher than that of example 1.
In the case of the example 3, the following examples are given,
a high energy density alkaline iron-sulfur flow battery: k of positive active material of flow battery is 0.1mol/L 4 Fe(CN) 6 And 0.1mol/L of Na 4 Fe(CN) 6 The supporting electrolyte is 1.0mol/L KOH; k of 1.0mol/L as a negative electrode active material 2 S, supporting electrolyte is 0.5mol/L KOH, and 1.0mol/L KCl is added to serve as auxiliary ions to adjust positive and negative electrolytes; the diaphragm adopts modified Nafion conduction K + A diaphragm; the positive electrode material uses carbon felt, and the negative electrode material uses modified nickel net. Wherein, the modified Nafion conducts K + Preparing a diaphragm: carrying out constant-temperature heating treatment on the ion exchange membrane by KOH with the concentration of 2.0M, wherein the heating temperature is 100 ℃, the heating time is 0.5h, and after the ionization process is finished, cleaning the ion exchange membrane by using deionized water and soaking the ion exchange membrane in the deionized water to obtain K + Forming an ion exchange membrane, and finally soaking in a KCl solution with the concentration of 1.0M for later use.
The alkaline iron-sulfur flow battery of example 3 was subjected to constant current charge-discharge cycling performance test, the flow rates of the positive electrolyte and the negative electrolyte were both 20mL/min, and charging was carried outThe electric cut-off voltage was 1.2V, the discharge cut-off voltage was 0.6V, and the current density was 20mA/cm 2 As shown in fig. 2 to 4, the average coulombic efficiency of the flow battery system in this embodiment is 99.7%, the average voltage efficiency is 85.1%, and the average energy efficiency is 85.4%.
The effect of improving the performance of the battery after addition of the auxiliary ion can be seen in example 1 in comparison with example 2. Comparison of example 2 and example 3 shows that the performance of the battery is further improved by using the modified nickel mesh.
In the case of the example 4, the following examples are given,
a high energy density alkaline iron-sulfur flow battery: k of positive active material of flow battery is 0.25mol/L 4 Fe(CN) 6 And 0.25mol/L of Na 4 Fe(CN) 6 The supporting electrolyte is KOH and NaOH, the molar ratio is 1:1, and the total molar concentration is 6.0 mol/L; k of 2.0mol/L as a negative electrode active material 2 S, supporting electrolyte is 6.0mol/L KOH, and 0.1mol/L KCl is added to serve as auxiliary ions to adjust positive and negative electrolytes; the separator is a porous separator; the positive electrode material uses carbon felt, and the negative electrode material uses modified nickel net.
The alkaline iron-sulfur flow battery of example 4 was subjected to constant current charge-discharge cycling performance test, with the flow rates of the positive electrolyte and the negative electrolyte being 20mL/min, the charge cut-off voltage being 1.2V, the discharge cut-off voltage being 0.6V, and the current density being 20mA/cm 2 As shown in fig. 6, the average coulombic efficiency of the flow battery system in this example was 98.3%, the average voltage efficiency was 87.8%, and the average energy efficiency was 88.4%. The above data indicate that the use of porous membranes does not affect the cycling stability of the cell, demonstrating the wide adaptability of the present system to separator use.
In the case of the example 5, the following examples were conducted,
a high energy density alkaline iron-sulfur flow battery: k of positive active material of flow battery is 0.85mol/L 4 Fe(CN) 6 And 0.85mol/L of Na 4 Fe(CN) 6 Namely the concentration of the ferrous cyanide ion is 1.7M; the anode-side supporting electrolyte is KOH and NaOH, the molar ratio is 1:6, and the total concentration is 0.1 mol/L. K of 2.0mol/L as a negative electrode active material 2 S, supporting electrolytes are KOH and NaOH in molar ratioThe total concentration is 6:1, 2.0mol/L, and 2.0mol/L KCl is added as auxiliary ions to adjust the electrolytes of the positive electrode and the negative electrode; the diaphragm adopts modified Nafion conduction K + A diaphragm; the positive electrode material uses carbon felt, and the negative electrode material uses modified nickel net.
The alkaline iron-sulfur flow battery of example 5 was subjected to constant current charge-discharge cycling performance test, with the flow rates of the positive electrolyte and the negative electrolyte being 20mL/min, the charge cut-off voltage being 1.2V, the discharge cut-off voltage being 0.6V, and the current density being 20mA/cm 2 As shown in fig. 7, the average coulombic efficiency of the flow battery system in this example was 99.7%, the average voltage efficiency was 85.0%, and the average energy efficiency was 85.3%.
The invention successfully increases the concentration of ferricyanide/ferrocyanide on the positive electrode side to 1.7M, which means that the volume capacity of the positive electrode side is 45.56Ah/L, while for a single concentration of potassium ferrocyanide, the solubility in pure water is 0.76M, i.e. 20.37Ah/L, which means that under the condition of more difficult dissolution, the volume capacity of the iron compound constructed by the embodiment of the invention is more than 2 times of the conventional volume capacity. Meanwhile, the auxiliary ion regulation and control strategy further constructed by the invention enhances the circulation stability of the iron-sulfur flow battery, so that the battery can be kept stable for a long time, and the service life of the battery is far longer than that of a conventional iron-sulfur battery system.
In the case of the example 6, it is shown,
a high energy density alkaline iron-sulfur flow battery: the positive active material of the flow battery adopts 0.74mol/L K 4 Fe(CN) 6 And 0.74mol/L of Na 4 Fe(CN) 6 Namely the concentration of the ferrous cyanide ion is 1.48M; the positive electrode side supported electrolyte was 0.5mol/L KOH. K of negative electrode active material of 15.0mol/L 2 S, the support electrolyte on the negative electrode side is 0.5mol/L KOH, and 1.0mol/L KCl is added to serve as auxiliary ions to adjust the electrolytes of the positive electrode and the negative electrode; the diaphragm adopts modified Nafion conduction K + A diaphragm; the positive electrode material uses carbon felt, and the negative electrode material uses modified nickel net.
The alkaline iron-sulfur flow battery of example 6 was subjected to constant current charge-discharge cycling performance test, the flow rates of the positive electrolyte and the negative electrolyte were both 20mL/min, and the charge cut-off voltage was 13V, discharge cut-off voltage of 0.4V, current density of 20mA/cm 2 As shown in fig. 8, in the flow battery system of this embodiment, the average coulombic efficiency is 98.9%, the average voltage efficiency is 69.3%, and the average energy efficiency is 70.1%, and the high-concentration active material is used on both sides of the positive electrode and the negative electrode, and the flow battery system has a high volume capacity characteristic.
When the polysulfide is at a higher concentration, the reaction rate at the electrode is not in time due to its own increased concentration, and the viscosity of the electrolyte increases, so the time from the reservoir to the electrode will also be extended. The invention solves the problem of poor battery cycle stability caused by polysulfide shuttling effect under high concentration, and improves the stability of a battery system.
In the case of the example 7, the following examples are given,
a high energy density alkaline iron-sulfur flow battery: the positive active material of the flow battery adopts 0.1mol/L K 4 Fe(CN) 6 And 0.1mol/L of Na 4 Fe(CN) 6 The supporting electrolyte is LiOH, KOH and NaOH, the molar ratio is kept in the range of 1:1: 1-6: 3:1, and the total concentration is 2.0M; k of 1.0mol/L as a negative electrode active material 2 S, supporting electrolyte is 0.5mol/L KOH, and 1.0mol/L KCl is added to serve as auxiliary ions to adjust positive and negative electrolytes; the diaphragm adopts modified Nafion conduction K + A diaphragm; the positive electrode material uses carbon felt, and the negative electrode material uses modified nickel net.
The alkaline iron-sulfur flow battery of example 7 was subjected to constant current charge-discharge cycling performance test, with the flow rates of the positive electrolyte and the negative electrolyte being 20mL/min, the charge cut-off voltage being 1.2V, the discharge cut-off voltage being 0.4V, and the current density being 20mA/cm 2 As shown in FIG. 9, in this example, when the molar ratio of LiOH, KOH and NaOH was 1:2:2, the average energy efficiency of the system was 88.45%.
In the case of the example 8, the following examples are given,
a high energy density alkaline iron-sulfur flow battery: the flow battery stack system consists of 9 single cells, and the positive active material is 20L of K of 0.1mol/L 4 Fe(CN) 6 And 0.1mol/L of Na 4 Fe(CN) 6 The supporting electrolyte is 1.0mol/L KOH; 1.0m of 40L of negative electrode active materialol/L of K 2 S, supporting electrolyte is 0.5mol/L KOH, and 1.0mol/L KCl is added to serve as auxiliary ions to adjust positive and negative electrolytes; the diaphragm adopts modified Nafion conduction K + A diaphragm; the anode and cathode electrode materials are carbon felts.
The alkaline iron-sulfur flow battery pair of example 8 was subjected to constant current charge-discharge cycle performance testing with a charge cut-off voltage of 11.7V, a discharge cut-off voltage of 4.5V, and a current density of 20mA/cm 2 (ii) a As shown in fig. 10, the average coulombic efficiency of the flow battery system in this example was 99.4%, the average voltage efficiency was 85.8%, and the average energy efficiency was 86.3%. Example 8 demonstrates the feasibility of using the galvanic pile in practical energy storage for the system of the present invention, and provides a basis for subsequent practical applications.
In the case of the embodiment 9, the following examples,
a high energy density alkaline iron-sulfur flow battery: k of positive active material of flow battery is 0.85mol/L 4 Fe(CN) 6 And 0.85mol/L of Na 4 Fe(CN) 6 The supporting electrolyte is 0.5mol/L KOH; k of 2.0mol/L of negative electrode active material 2 S, 0.5mol/L KOH supporting electrolyte; and adding 1.0M of electrolyte into the positive and negative electrodesKClAs positive and negative regulating ions; the diaphragm adopts modified Nafion conduction K + A diaphragm; the positive electrode material uses carbon felt, the negative electrode material uses MoS 2 And (3) modifying the electrode.
The alkaline iron-sulfur flow battery of example 9 was subjected to constant current charge-discharge cycling performance test, and the flow rates of the positive electrolyte and the negative electrolyte were both 20mL/min, the charge cut-off voltage was 1.2V, the discharge cut-off voltage was 0.6V, and the current density was 20mA/cm 2 As shown in fig. 11, the average coulomb efficiency of the flow battery system in this embodiment is 99.1%, the average voltage efficiency is 88.0%, and the average energy efficiency is 88.7%.
MoS 2 Is a typical transition metal disulfide, is a graphite-like two-dimensional layered material, and retains the excellent performance of a two-dimensional structure in a form of a nano-sheet structure when growing on the surface of a carbon material substrate. MoS 2 There are two main phase structures, 2H phase (2H-MoS) 2 ) And 1T phase (1T-MoS) 2 ). Sodium (A)MoS of rice structure 2 Has larger specific surface area, stronger adsorption capacity and better catalytic performance. Furthermore, MoS 2 There is a wide layer spacing that can provide a channel for electron transport and active species transport. Growth of MoS on virgin carbon felt 2 Capable of accelerating polysulfide reaction kinetics, on the one hand, thanks to MoS 2 The catalyst has catalytic activity, and is mainly shown in that the catalyst can promote the reaction rate of polysulfide on an electrode and reduce the overpotential and the reaction energy barrier of the reaction; another aspect is MoS 2 The unique layered structure may provide a channel for the transport of active substances.
In the light of the above example 10,
a high energy density alkaline iron-sulfur flow battery: k of positive active material of flow battery is 0.1mol/L 3 Fe(CN) 6 Na as a supporting electrolyte in an amount of 0.1mol/L 2 O; k of 0.1mol/L as a negative electrode active material 2 S, 0.1mol/L Na as supporting electrolyte 2 O, and adding 1.0mol/L of KBr or K 2 SO 4 As auxiliary ions to adjust positive and negative electrolytes; the diaphragm is a ceramic membrane; the positive electrode material uses carbon felt, and the negative electrode material uses CuS modified electrode.
The alkaline iron-sulfur flow battery of example 10 was subjected to constant current charge-discharge cycling performance test, with the flow rates of the positive electrolyte and the negative electrolyte being 20mL/min, the charge cut-off voltage being 1.2V, the discharge cut-off voltage being 0.6V, and the current density being 20mA/cm 2 As shown in fig. 12, the average voltage efficiency of the flow battery system in this example was 86.8%, and the average energy efficiency was 85.6%.
In the case of the embodiment 11, the following examples are given,
a high energy density alkaline iron-sulfur flow battery: the positive active material of the flow battery adopts 0.1mol/L K 4 Fe(CN) 6 And 0.1mol/L of Na 4 Fe(CN) 6 The supporting electrolyte is LiOH, KOH and NaOH, the molar ratio is 1:2:2, and the total concentration is 0.5M; k of 1.0mol/L as a negative electrode active material 2 S, the supporting electrolyte is LiOH, KOH and NaOH, the molar ratio is 1:2:2, the total concentration is 0.5M, and 1.0mol/L KCl is added as an auxiliary ion to adjust the positive electrolyte and the negative electrolyte; the diaphragm adopts modified Nafion conduction K + A diaphragm; the positive electrode material uses carbon felt, and the negative electrode material uses modified nickel net.
The alkaline iron-sulfur flow battery of example 11 was subjected to constant current charge-discharge cycling performance test, and the flow rates of the positive electrolyte and the negative electrolyte were both 20mL/min, the charge cut-off voltage was 1.2V, the discharge cut-off voltage was 0.4V, and the current density was 20mA/cm 2 As shown in fig. 13, the average coulomb efficiency of the flow battery system in this embodiment is 99.6%, the average voltage efficiency is 84.8%, and the average energy efficiency is 85.2%.
In accordance with example 12, there is provided,
a high energy density alkaline iron-sulfur flow battery: the positive active material of the flow battery adopts 0.1mol/L K 4 Fe(CN) 6 And 0.1mol/L of Na 4 Fe(CN) 6 The supporting electrolyte is LiOH, KOH and NaOH, the molar ratio is 1:2:2, and the total concentration is 5.0M; k of 1.0mol/L of negative electrode active material 2 S, the supporting electrolyte is LiOH, KOH and NaOH, the molar ratio is 1:2:2, the total concentration is 5.0M, and 1.0mol/L KCl is added as an auxiliary ion to adjust the positive electrolyte and the negative electrolyte; the diaphragm adopts modified Nafion conduction K + A diaphragm; the positive electrode material uses carbon felt, and the negative electrode material uses modified nickel net.
The alkaline iron-sulfur flow battery of example 12 was subjected to constant current charge-discharge cycling performance test, and the flow rates of the positive electrolyte and the negative electrolyte were both 20mL/min, the charge cut-off voltage was 1.2V, the discharge cut-off voltage was 0.4V, and the current density was 20mA/cm 2 As shown in fig. 14, the average coulomb efficiency of the flow battery system in this embodiment is 99.8%, the average voltage efficiency is 86.0%, and the average energy efficiency is 86.1%.
In accordance with example 13, there is provided,
a high energy density alkaline iron-sulfur flow battery: the positive active material of the flow battery adopts 0.1mol/L K 4 Fe(CN) 6 And 0.1mol/L of Na 4 Fe(CN) 6 The supporting electrolyte is LiOH, NaOH, KOH or NH 3 ·H 2 O, the molar ratio is 1:1:1:1, and the total concentration is 0.5M; k of 1.0mol/L as a negative electrode active material 2 S, supporting electrolyte is LiOH, NaOH, KOH, NH 3 ·H 2 O, the molar ratio is 1:2:1:2, the total concentration is 4.0M, and 1.0mol/L KCl is added as auxiliary ions to adjust the electrolytes of the positive electrode and the negative electrode; the diaphragm adopts modified Nafion conduction K + A diaphragm; the positive electrode material uses carbon felt, and the negative electrode material uses modified nickel net.
The alkaline iron-sulfur flow battery of example 13 was subjected to constant current charge-discharge cycling performance tests, with the flow rates of the positive and negative electrolytes both being 20mL/min, the charge cut-off voltage being 1.2V, the discharge cut-off voltage being 0.4V, and the current density being 20mA/cm 2 As shown in fig. 15, the average coulombic efficiency of the flow battery system in this example was 99.3%, the average voltage efficiency was 85.1%, and the average energy efficiency was 85.7%.
In the case of the example 14, the following examples are given,
a high energy density alkaline iron-sulfur flow battery: the positive active material of the flow battery adopts 0.1mol/L K 4 Fe(CN) 6 And 0.1mol/L of Na 4 Fe(CN) 6 The supporting electrolyte is LiOH, NaOH, KOH or NH 3 ·H 2 O, the molar ratio is 6:1:1:1, and the total concentration is 2.0M; k of 1.0mol/L as a negative electrode active material 2 S, supporting electrolyte is LiOH, NaOH, KOH, NH 3 ·H 2 O, the molar ratio is 6:1:1:1, the total concentration is 2.0M, and 1.0mol/L KCl is added as auxiliary ions to adjust the electrolytes of the positive electrode and the negative electrode; the diaphragm adopts modified Nafion conduction K + A diaphragm; the positive electrode material uses carbon felt, and the negative electrode material uses modified nickel net.
The alkaline iron-sulfur flow battery of example 14 was subjected to constant current charge-discharge cycling performance tests, and the flow rates of the positive electrolyte and the negative electrolyte were both 20mL/min, the charge cut-off voltage was 1.2V, the discharge cut-off voltage was 0.4V, and the current density was 20mA/cm 2 As shown in fig. 16, the average coulombic efficiency of the flow battery system in this example was 99.3%, the average voltage efficiency was 84.2%, and the average energy efficiency was 85.8%.
In accordance with example 15, there is provided,
a high energy density alkaline iron-sulfur flow battery: the positive active material of the flow battery adopts 0.1mol/L Li 4 Fe(CN) 6 And 0.1mol/L of Na 4 Fe(CN) 6 LiHCO with 2.0M supporting electrolyte 3 (ii) a 1.0mol/L of lithium polysulfide as a negative electrode active material and 2.0M of Li as a supporting electrolyte 2 HCO 3 Adding 1.0mol/L LiI as auxiliary ions to adjust positive and negative electrolytes; the diaphragm adopts a modified SPEEK diaphragm to conduct Li + A diaphragm; the positive electrode material uses carbon felt, the negative electrode material uses SnS 2 And (3) modifying the electrode.
The alkaline iron-sulfur flow battery of example 15 was subjected to constant current charge-discharge cycling performance test, and the flow rates of the positive electrolyte and the negative electrolyte were both 20mL/min, the charge cut-off voltage was 1.2V, the discharge cut-off voltage was 0.4V, and the current density was 20mA/cm 2 As shown in fig. 17, the average coulombic efficiency of the flow battery system in this example was 99.4%, the average voltage efficiency was 85.1%, and the average energy efficiency was 85.6%.
In the example of the method of manufacturing the composite material of the present invention 16,
a high energy density alkaline iron-sulfur flow battery: k of positive active material of flow battery is 0.1mol/L 4 Fe(CN) 6 And 0.1mol/L of Na 4 Fe(CN) 6 The supporting electrolyte is 1.0mol/L NaOH; 1.0mol/L of Na as a negative electrode active material 2 S 2 The supporting electrolyte is 0.5mol/L NaOH, and 1.0mol/L NaCl is added to serve as auxiliary ions to adjust the positive electrolyte and the negative electrolyte; the membrane adopts modified Nafion to conduct Na + A diaphragm; the positive electrode material uses carbon felt, and the negative electrode material uses modified nickel net.
The alkaline iron-sulfur flow battery of example 16 was subjected to constant current charge-discharge cycling performance test, and the flow rates of the positive electrolyte and the negative electrolyte were both 20mL/min, the charge cut-off voltage was 1.2V, the discharge cut-off voltage was 0.6V, and the current density was 20mA/cm 2 As shown in fig. 18, the average coulombic efficiency of the flow battery system in this example was 99.3%, the average voltage efficiency was 84.2%, and the average energy efficiency was 84.8%.
The embodiment of the invention constructs a strategy for regulating the stability of the active substances by the same type of ions, and the diaphragm is soaked in the related solution, so that a foundation is laid for the subsequent strategy for regulating the stability of the active substances by the same type of ions, and the stability of the active substances by the same type of ions is added; meanwhile, the species, quantity and proportion of the auxiliary ions are adjusted. On one hand, the method is used for regulating and controlling the solubility of the ferricyanide/ferrocyanide on the positive electrode side, on the other hand, the method is used for stabilizing polysulfide, the shuttle effect of low polysulfide ions is realized, and finally, the battery system with stable long-term operation is constructed. The invention successfully inhibits the shuttle effect of polysulfide, greatly improves the solubility of ferricyanide/ferrocyanide and constructs an alkaline flow battery system with high energy density and long cycle life by constructing a strategy that auxiliary ions are consistent with active material cations.
In the comparative example 1,
k of positive electrode active substance of flow battery is 0.1mol/L 4 Fe(CN) 6 And 0.1mol/L of Na 4 Fe(CN) 6 The supporting electrolyte is 1.0mol/L NaOH; k of 1.0mol/L as a negative electrode active material 2 S, NaOH with supporting electrolyte of 0.5 mol/L; the membrane adopts modified Nafion to conduct Na + A diaphragm; carbon felt is used as the anode and cathode materials.
The alkaline iron-sulfur flow battery of comparative example 1 was subjected to constant current charge-discharge cycling performance test, the flow rates of the positive electrolyte and the negative electrolyte were both 20mL/min, the charge cut-off voltage was 1.3V, the discharge cut-off voltage was 0.4V, and the current density was 20mA/cm 2 . As shown in fig. 19, the cell in this comparative example had high internal resistance and large polarization, and the cell could not be normally cycled. On one hand, because the negative electrode uses the carbon felt, the lower catalytic reaction speed of polysulfide is a key influence factor for limiting the lower overall reaction rate of the battery, the reaction kinetics of the carbon felt on the polysulfide cannot achieve a faster effect, and the polarization of the battery is larger in the battery circulation process. Meanwhile, due to the difference between the cations of the negative electrode supporting electrolyte and the active material in the embodiment, sodium ions are continuously accumulated on the diaphragm in the battery circulation process, and the diaphragm is a potassium ion type conduction diaphragm, so that the polarization of the battery is relatively large.
In a comparative example 2,
the positive electrode electrolyte is 1.0mol/L K 4 Fe(CN) 6 The supporting electrolyte is NaCl; the electrolyte of the negative electrode is 1.0mol/L of Na 2 S 2 The supporting electrolyte is NaCl, as described in detail in The literature (Journal of The Electrochemical Society, 163, A5150-A5153, 2016). The diaphragm adopts modified Nafion conduction K + A diaphragm; carbon felts are used as the anode and cathode electrode materials.
The flow rates of the positive electrode electrolyte and the negative electrode electrolyte of comparative example 2 were both 20mL/min, the charge cut-off voltage was 1.3V, the discharge cut-off voltage was 0.4V, and the current density was 20mA/cm 2 . The long-term stable circulation of the battery is difficult to realize, because the auxiliary ions are inconsistent with the cations of the active substances and the conductivities of the auxiliary ions and the active substances are inconsistent, the ions are continuously accumulated at the diaphragm, the polarization of the battery is continuously increased in the circulation process, the circulation stability of the battery is finally deteriorated, and the long-term operation is difficult to realize.
In the comparative example 3,
the positive electrode electrolyte is 0.4mol/L K 4 Fe(CN) 6 The supporting electrolyte is 1.0mol/L KOH; k of 1.0mol/L as a negative electrode active material 2 S, 0.5mol/L KOH supporting electrolyte; the diaphragm adopts modified Nafion conduction K + A diaphragm; the positive electrode uses carbon felt as an electrode, and the negative electrode uses a modified nickel screen as an electrode.
The alkaline iron-sulfur flow battery of comparative example 3 was tested for constant current charge-discharge cycling performance, with the flow rates of both the positive electrolyte and the negative electrolyte being 20mL/min, the charge cut-off voltage being 1.3V, the discharge cut-off voltage being 0.4V, and the current density being 20mA/cm 2 . As shown in fig. 20, the cell in this comparative example was operable, but the volume capacity was low due to the low concentration of potassium ferrocyanide on the positive electrode side. In practical applications, the iron-sulfur flow battery is limited by the low solubility of the ferricyanide/ferrocyanide on the positive side. Many literature references have ferricyanide/ferrocyanide solubility of only 0.4M (e.g., Science, 349, 1529-1532, 2015; Nature Energy, 1, 16102, 2016; Advanced Energy Materials, 9, 1900039, 2019), which is apparently difficult to meet with practical requirements.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (10)

1. A high-energy-density alkaline iron-sulfur flow battery comprises a positive electrolyte, a negative electrolyte, a diaphragm, a positive electrode and a negative electrode, and is characterized in that an active substance in the positive electrolyte is ferricyanide or ferricyanide ions, and the concentration of the active substance on the positive side is 0.1-1.7M;
the active substance in the negative electrode electrolyte is a sulfide solution, and the concentration range of the negative electrode active substance is 0.1-15M;
the supporting electrolyte in the positive and negative electrolytes is LiOH, NaOH, KOH or NH with the molar concentration of 0.1-6M 3 ·H 2 O、NH 4 HCO 3 、(NH 4 ) 2 CO 3、 Li 2 CO 3 、LiHCO 3 、Na 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 、Li 2 O、Na 2 O or K 2 One or more of O; when there are several kinds of supporting electrolytes for both the positive and negative electrodes, it is necessary to ensure that the supporting electrolytes for both the positive and negative electrodes have a common cation;
the diaphragm is any one of a porous membrane, a ceramic membrane or an ion exchange membrane subjected to ionization treatment;
the concentration range of the regulating ions in the positive and negative electrolyte is 0.1-2.0M, and the regulating ions are the same as the positive ions of the negative active material and the supporting electrolyte.
2. The high energy density alkaline iron-sulfur flow battery as claimed in claim 1, wherein the positive and negative electrodes are carbon cloth, carbon paper, carbon felt, graphite plate, graphene modified carbon felt, graphite alkyne modified carbon felt, nickel mesh, modified nickel mesh, CuS 2 Modified electrode, CuS modified electrode, MoS 2 Modified electrode, CoS 2 Modified electrode, CoS modified electrode, NiS modified electrode, PbS modified electrode, SnS 2 Modified electrode, VS 2 Modified electrode, WS 2 Modified electrodes or FeS 2 Any one of the modified electrodes.
3. The high energy density alkaline iron-sulfur flow battery of claim 1, wherein the ion exchange membrane is any one of perfluorinated sulfonic acid membrane, sulfonated polyether ether ketone membrane, sulfonated polyimide membrane, sulfonated polyfluorene ether ketone membrane, polyvinylidene fluoride membrane, polyethersulfone membrane, sulfonated polyaryletherketone membrane, polysulfone fiber membrane, polyphthalazinone ether ketone membrane, sulfonated polyethersulfone membrane, tetrafluoroethylene membrane, polystyrene membrane, polyethylene membrane, polyphenylene membrane, polybenzimidazole membrane, sulfonated polyaryletherketone membrane, polyparaphenylene membrane, sulfonated polydiallylbisphenol ether ketone membrane, polyfluorenyl ether ketone sulfone membrane, polyfluorenyl ether membrane, polyvinyl chloride acylated membrane, polyphenyl ether membrane or polyphenyl ether membrane.
4. The high energy density alkaline iron-sulfur flow battery of claim 1, wherein the sulfide solution is one or more of potassium sulfide, potassium polysulfide, sodium sulfide, sodium polysulfide, lithium sulfide, lithium polysulfide, calcium sulfide, calcium polysulfide, rubidium sulfide, cesium sulfide, aluminum sulfide, magnesium sulfide, zinc sulfide, benzenesulfonic acid, thiol, thiophenol, or thioether mixed in any mass ratio.
5. The high energy density alkaline iron-sulfur flow battery as claimed in claim 1, wherein when two supporting electrolytes are used in the positive and negative electrolytes, the total molar concentration is 0.1M to 6M, and the molar ratio of the two supporting electrolytes is 1/6 to 6/1.
6. The high energy density alkaline iron-sulfur flow battery as claimed in claim 1, wherein when the number of supporting electrolytes in the positive and negative electrolytes is three, the total molar concentration is 0.5M to 5.0M, and the molar ratio of the three supporting electrolytes is in the range of 1:1:1 to 6:3: 1.
7. The high energy density alkaline iron-sulfur flow battery as claimed in claim 1, wherein when the number of supporting electrolytes in the positive and negative electrolytes is four, the total molar concentration is 0.5M to 4.0M, and the molar ratio of the four supporting electrolytes is in the range of 1:1:1:1 to 6:1: 1.
8. The method of making a high energy density alkaline iron-sulfur flow battery of claim 1, comprising the steps of:
preparing a diaphragm: the diaphragm is any one of an ion exchange membrane, a porous membrane or a ceramic membrane; when the diaphragm is an ion exchange membrane, carrying out ionization treatment;
preparing an electrode: carbon cloth, carbon paper, carbon felt, graphite plate, graphene modified carbon felt, graphite alkyne modified carbon felt, nickel net, modified nickel net and CuS 2 Modified electrode, CuS modified electrode, MoS 2 Modified electrode, CoS 2 Modified electrode, CoS modified electrode, NiS modified electrode, PbS modified electrode, SnS 2 Modified electrode, VS 2 Modified electrode, WS 2 Modified electrodes or FeS 2 The modified electrode is used as an electrode material of a battery;
preparing a negative electrode electrolyte: dissolving potassium sulfide, potassium polysulfide, sodium sulfide, sodium polysulfide, lithium sulfide, lithium polysulfide, calcium sulfide, calcium polysulfide, rubidium sulfide, cesium sulfide, aluminum sulfide, magnesium sulfide, zinc sulfide, benzenesulfonic acid, mercaptan, thiophenol or thioether in an alkaline solution to obtain an alkaline solution of sulfide; adding 0.1-2.0M of regulating ions, wherein the regulating ions are LiCl, KCl, NaCl, LiBr, KBr, NaBr, LiI, KI, NaI and Li 2 SO 4 、LiNO 3 、K 2 SO 4 、KNO 3 、Na 2 SO 4 、NaNO 3 、NH 4 Cl or (NH) 4 ) 2 SO 4 Any one or more of the solutions are mixed, and a magnetic stirrer is used for fully stirring and dissolving;
preparing a positive electrolyte: dissolving one or more of potassium ferricyanide, potassium ferrocyanide, sodium ferricyanide, ammonium ferrocyanide, lithium ferricyanide or lithium ferrocyanide in alkaline solution to obtain a solutionAn alkaline solution of ferricyanide/ferrocyanide; adding 0.1-2.0M of regulating ions, wherein the regulating ions are LiCl, KCl, NaCl, LiBr, KBr, NaBr, LiI, KI, NaI and Li 2 SO 4 、LiNO 3 、K 2 SO 4 、KNO 3 、Na 2 SO 4 、NaNO 3 、NH 4 Cl or (NH) 4 ) 2 SO 4 Any one or more of the solutions are mixed, and a magnetic stirrer is used for fully stirring and dissolving;
and assembling the prepared positive and negative electrolytes, the diaphragm and the positive and negative electrodes into the alkaline redox flow battery.
9. The method for preparing the high-energy-density alkaline iron-sulfur flow battery as claimed in claim 8, wherein the alkaline solution in the preparation of the negative electrolyte and the preparation of the positive electrolyte is a supporting electrolyte, and the preparation method comprises the following steps: preparing LiOH, NaOH, KOH and NH by using deionized water 3 ·H 2 O、NH 4 HCO 3 、(NH 4 ) 2 CO 3、 Li 2 CO 3 、Li 2 HCO 3 、Na 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 、Li 2 O、Na 2 O or K 2 O, one or more alkali solutions with the total molar concentration of 0.1-6M; when there are several supporting electrolytes for both positive and negative electrodes, it is necessary to ensure that the supporting electrolytes for both positive and negative electrodes have a common cation.
10. The method for preparing a high energy density alkaline iron-sulfur flow battery as claimed in claim 8, wherein in the preparation of the diaphragm, the ionization treatment of an ion exchange membrane: passing through LiOH, NaOH, KOH and NH with the concentration of 0.1-6.0M 3 ·H 2 O、NH 4 HCO 3 、(NH 4 ) 2 CO 3 、Li 2 CO 3 、Li 2 HCO 3 、Na 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 、Li 2 O、Na 2 O or K 2 Carrying out constant-temperature heating treatment on the ion exchange membrane by any alkali solution in O at the heating temperature of 40-100 ℃ for 0.5-8 h, cleaning by using deionized water after the ionization process is finished, and soaking in the deionized water to obtain K + 、Na + 、Li + Or NH 4 + Forming an ion exchange membrane, and finally soaking the membrane in LiCl, KCl, NaCl, LiBr, KBr, NaBr, LiI, KI, NaI and Li with the concentration of 0.1-2.0M 2 SO 4 、LiNO 3 、K 2 SO 4 、KNO 3 、Na 2 SO 4 、NaNO 3 、NH 4 Cl、NH 4 Br or (NH) 4 ) 2 SO 4 The solution is ready for use.
CN202210897479.8A 2022-07-28 2022-07-28 High-energy-density alkaline iron-sulfur flow battery and preparation method thereof Pending CN115000480A (en)

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