CN112103546A - Double-electronic compound flow battery system based on salt caverns - Google Patents
Double-electronic compound flow battery system based on salt caverns Download PDFInfo
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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
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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- C07D213/32—Sulfur atoms
- C07D213/34—Sulfur atoms to which a second hetero atom is attached
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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
- H01M2300/00—Electrolytes
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a salt-hole-based two-electron compound flow battery system which comprises a positive electrode active substance and a negative electrode active substance, wherein TEMPO-4-sodium sulfonate is used as the positive electrode active substance, an asymmetric two-electron viologen compound is used as the negative electrode active substance, the positive electrode active substance and the negative electrode active substance are easy to prepare, the reaction condition is mild, the synthetic route is short, and the cost is low. The double-electron compound flow battery system can be suitable for the battery environment of a salt cavern system, and has the advantages of environmental friendliness, high circulation efficiency, adjustable properties and the like.
Description
Technical Field
The invention relates to the field of flow batteries, in particular to a double-electronic compound flow battery system.
Background
In the world today, energy is an important material basis for human survival and development and an important factor for promoting economic development. With the rapid development of human economy, the consumption of traditional fossil energy is increasing day by day, which brings serious environmental pollution, so that the development of renewable energy becomes an indispensable way. However, the renewable energy sources have the characteristics of discontinuity, instability, limitation by regional environment and difficult grid connection, so that the utilization rate is low, the wind and light abandoning rate is high, and resources are wasted. There is a need for a robust development of efficient, inexpensive, safe and reliable energy storage technology that can be used in conjunction therewith.
The redox flow battery has the characteristics of high safety, large energy storage scale, high efficiency, long service life and the like, has good application prospect in the field of large-scale energy storage, has higher energy capacity compared with a capacitor and a solid-state battery, stores battery energy in electrolyte of active substances, stores the electrolyte in a liquid storage tank, and circularly enters a battery chamber through a pump. During the charging and discharging process, the flowing electrolyte conveys the electrolyte to the battery chamber to generate electrochemical reaction, thereby realizing the conversion between chemical energy and electric energy. The special structure is very suitable for large-scale storage energy storage requirements, and the content of the electrolyte can be adjusted according to the energy. The traditional flow battery utilizes inorganic materials as active substances (such as vanadium flow batteries), however, the disadvantages of high cost, toxicity, limited resources, formation of dendrites, low electrochemical activity and the like of the inorganic materials limit the large-scale application of organic active substances of the flow battery, and the organic active substances have the advantages of low cost, "green", rich resources, easy adjustment of molecular energy level, fast electrochemical reaction and the like, and have attracted extensive attention at home and abroad.
The electrolyte of the water-based organic flow battery has the advantage of incombustibility and is safer to operate. In addition, in the water-based organic flow battery, the conductivity of the electrolyte is high, the electrochemical reaction rate is high, and the output power is high. Therefore, the water-based organic flow battery is an ideal large-scale energy storage technology. At present, the aqueous phase organic flow battery still faces some challenges, such as limited solubility of active materials (organic matters), easy cross contamination of electrolyte, low operating current density, easy occurrence of side reaction of water electrolysis, and the like. Therefore, development of a new organic active material to overcome the above disadvantages is of great significance for expanding the chemical space (e.g., open circuit voltage, energy density, stability, etc.) of the organic flow battery.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art.
Therefore, the invention provides a double-electron compound flow battery system based on salt holes, the flow battery system comprises TEMPO-4-sulfonic acid sodium salt and an asymmetric double-electron viologen compound, the TEMPO-4-sulfonic acid sodium salt can be used as an anode active substance, the asymmetric double-electron viologen compound can be used as a cathode active substance, and in the charging and discharging processes, a cheap permeable membrane is selected as an ion exchange isolation membrane, so that the cost of the battery is reduced, the ion permeability of the battery is improved, and the effective discharge capacity and the energy efficiency of the flow battery system are further improved.
The two-electron compound flow battery system comprises a positive electrode active material and a negative electrode active material, wherein TEMPO-4-sulfonic acid sodium salt is used as the positive electrode active material, an asymmetric two-electron viologen compound is used as the negative electrode active material, and the TEMPO-4-sulfonic acid sodium salt has a chemical structural formula as follows:
wherein 4-OH-TEMPO is used as the most main redox active site, and sulfonate is introduced on hydroxyl to increase the solubility of TEMPO derivative in aqueous solution; the acid type is obtained through one-step reaction of 4-OH-TEMPO and chlorosulfonic acid, and sodium salt is directly prepared through sodium bicarbonate neutralization;
the chemical structural formula of the asymmetric two-electron viologen compound is as follows:
wherein, the viologen compound is used as a main oxidation-reduction active site, and hydroxyl and sulfonic acid groups are respectively introduced into two N on the 4 th site and the 4' th site to increase the molecular hydrophilization of the viologen; the method has the advantages that 4, 4-bipyridine is used as a raw material, and the asymmetric double-electron viologen compound with double electron characteristics is obtained through a Menschutkin reaction.
According to the two-electron compound flow battery system, TEMPO-4-sulfonic acid sodium salt is used as a positive electrode active material, and an asymmetric two-electron purple crystal compound is used as a negative electrode active material. The positive active substance and the negative active substance are both small-molecule organic salts, so that the current density and the energy density of a flow battery system can be increased, and the double-electron compound flow battery with the outstanding advantages of strong stability, good safety, flexible configuration, high response speed, environmental friendliness and the like is obtained. Namely, the flow battery system has the advantages of easy preparation of active materials, high safety performance, high energy density, stable charge and discharge performance, high solubility of the active materials and the like.
According to one embodiment of the invention, the preparation of the TEMPO-4-sulfonic acid sodium salt comprises the following steps: taking 4-hydroxy-2, 2,6, 6-tetramethyl piperidinyloxy (hereinafter referred to as 4-OH-TEMPO) containing positive active molecules as a raw material, sulfonating chlorosulfonic acid, and then neutralizing by sodium bicarbonate to directly prepare TEMPO-4-sulfonic acid sodium salt, wherein the chemical reaction formula is shown as a formula (1):
according to one embodiment of the invention, the preparation of the TEMPO-4-sulfonic acid sodium salt comprises the following specific steps: dissolving 4-OH-TEMPO in dichloromethane, stirring at room temperature, dropwise adding chlorosulfonic acid, and stirring at room temperature for 5 minutes after the addition is finished. After the reaction was completed, a saturated sodium bicarbonate solution was added dropwise to adjust the pH of the resulting reaction solution to 7, and the unreacted 4-OH-TEMPO was removed by extraction twice with ethyl acetate. And (3) decompressing and spin-drying the solvent to obtain a mixture containing TEMPO-4-sulfonic acid sodium salt and sodium sulfonate, extracting TEMPO-4-sulfonic acid sodium salt in the mixed solid by using absolute ethyl alcohol, decompressing and removing the solvent to obtain yellow solid.
According to one embodiment of the present invention, chlorosulfonic acid is used as the sulfonation reagent, and concentrated sulfuric acid is used as the sulfonation reagent in the conventional sulfonation reaction, and the chemical reaction formula is shown as formula (2):
the method comprises the following steps: grinding 4-OH-TEMPO into powder, slowly adding into concentrated sulfuric acid for several times under stirring at room temperature, and continuously stirring at room temperature for 20 min after the addition. After completion of the reaction, the reaction mixture was slowly added dropwise to 1.1L of a saturated aqueous solution of sodium hydrogencarbonate. The resulting solution was extracted twice with ethyl acetate to remove unreacted 4-OH-TEMPO. And (3) decompressing and spin-drying the aqueous phase to obtain a mixture containing the sulfonate TEMPO and sodium sulfate, extracting the sulfonate TEMPO in the mixed solid by using acetone, decompressing and removing the solvent to obtain TEMPO-4-sulfonic acid sodium salt.
The traditional sulfonation reaction steps are complicated, and the particle size of the raw material, the amount of raw material added and the rate of neutralizing sulfuric acid all affect the yield of the final product. The chlorosulfonic acid is used for substituting concentrated sulfuric acid for sulfonation reaction, so that not only can complicated steps be omitted, but also the reaction can be completed in one step, and the reaction cost can be greatly reduced on the basis of not influencing the product yield.
According to one embodiment of the present invention, the preparation of the asymmetric two-electron viologen compound comprises the following steps: the method is characterized in that 4, 4-bipyridyl and hydroxyl-terminated substituted bromoalkyl alcohol are used as raw materials, a single substituted viologen compound is prepared through a Menschutkin reaction, the intermediate product and 1, 3-propane sultone continue to carry out the Menschutkin reaction, and an asymmetric type double-electron viologen compound is prepared, wherein the chemical reaction formula is shown as a formula (3):
wherein n represents the length of an alkyl chain and is one of 2-6;
according to one embodiment of the invention, the preparation of the asymmetric type two-electron viologen compound comprises the following specific steps:
dissolving 4, 4' -bipyridine in an acetonitrile solvent, adding alkyl bromide substituted by hydroxyl, heating to 90 ℃, refluxing, stirring and reacting, stopping heating after the reaction is completed, cooling to room temperature, cooling the obtained reaction liquid, performing suction filtration, washing the solid for 3 times, and finally performing vacuum drying to obtain a mono-substituted viologen compound;
and (2) mixing the mono-substituted viologen compound prepared in the step and 1, 3-propane sultone, adding an acetonitrile solvent, heating to 90 ℃, refluxing and stirring for reaction, stopping heating after the reaction is completed, cooling to room temperature, cooling the obtained reaction liquid, performing suction filtration, washing the solid for 3 times, and finally performing vacuum drying to obtain the asymmetric two-electron viologen compound.
According to an embodiment of the present invention, the aqueous nano-polymer flow battery system further includes: the electrolyte comprises two electrolyte liquid reservoirs, wherein the two electrolyte liquid reservoirs are arranged at intervals, each electrolyte liquid reservoir is a liquid storage tank for storing electrolyte or a salt cave which is formed after salt mine mining and is provided with a physical dissolution cavity, the electrolyte in one electrolyte liquid reservoir comprises the positive active substance and supporting electrolyte, the electrolyte in the other electrolyte liquid reservoir comprises the negative active substance and supporting electrolyte, and the positive active substance and the negative active substance are respectively directly dissolved or dispersed in a system taking water as a solvent in a bulk form; the flow battery stack comprises a battery diaphragm, the battery diaphragm divides the flow battery stack into an anode area and a cathode area which are distributed at intervals, the anode area is communicated with one electrolyte liquid storage tank, and the cathode area is communicated with the other electrolyte liquid storage tank.
According to one embodiment of the present invention, the concentration of the positive electrode active material is 0.2mol · L-1～6.0mol·L-1The concentration of the negative electrode active material is 0.1 mol.L-1～3.0mol·L-1。
According to one embodiment of the present invention, the electrolyte reservoir is a pressurized and sealed container having a pressure of 0.1 to 0.5 MPa.
According to one embodiment of the invention, an inert gas is introduced into the electrolyte reservoir to purge and maintain pressure.
According to one embodiment of the invention, the inert gas is nitrogen or argon.
According to one embodiment of the invention, the battery diaphragm is an anion exchange membrane, a cation exchange membrane or a polymer porous membrane with a pore size of 10nm to 300 nm.
According to one embodiment of the invention, the supporting electrolyte is a NaCl salt solution, a KCl salt solution, Na2SO4Salt solution, K2SO4Salt solution, MgCl2Salt solution, MgSO4Salt solution, CaCl2Salt solution, NH4At least one of a Cl salt solution.
According to one embodiment of the invention, the supporting electrolyte has a molar concentration of 0.1mol · L-1～8.0mol·L-1。
According to one embodiment of the invention, the anode region and the cathode region are respectively provided with electrodes, and the positive electrode and the negative electrode are carbon material electrodes.
According to one embodiment of the invention, the carbon material electrode is one or a composite of several of carbon felt, carbon paper, carbon cloth, carbon black, activated carbon fiber, activated carbon particles, graphene, graphite felt and glass carbon material.
According to one embodiment of the invention, the electrodes are formed as electrode plates, the thickness of the electrode plates being 2mm to 8 mm.
According to an embodiment of the present invention, the aqueous nano-polymer flow battery system further includes: and the current collectors are respectively arranged on two sides of the flow battery stack and can collect and conduct current generated by active substances of the flow battery stack to an external lead.
According to an embodiment of the invention, the current collector is one of a conductive metal plate, a graphite plate or a carbon-plastic composite plate.
According to one embodiment of the present invention, the conductive metal plate includes at least one metal of copper, nickel, and aluminum.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic structural view of a bi-electronic compound flow battery system according to an embodiment of the present invention;
FIG. 2 is 1- (2-hydroxy-ethyl) - [4, 4' -bipyridine according to example 2 of the present invention]Of 1-onium bromides1H NMR spectrum;
FIG. 3 is 1- (2-hydroxy-ethyl) - [4, 4' -bipyridine according to example 2 of the present invention]Of 1-onium bromides13C NMR spectrum;
FIG. 4 is 1- (2-hydroxy-ethyl) -1 '- (3-sulfo-propyl) - [4, 4' -bipyridine according to example 3 of the present invention]Of (E) -1, 1' -dibromides1H NMR spectrum;
FIG. 5 is 1- (2-hydroxy-ethyl) -1 '- (3-sulfo-propyl) - [4, 4' -bipyridine according to example 3 of the present invention]Of (E) -1, 1' -dibromides13C NMR spectrum;
FIG. 6 is a CV diagram at a scan speed of 20mV/s for TEMPO-sulfonic acid sodium salt (concentration of 4mM in aqueous sodium chloride solution at pH 7) according to example 1 of the present invention;
FIG. 7 is a CV diagram of 1- (2-hydroxy-ethyl) -1 ' - (3-sulfo-propyl) - [4,4 ' -bipyridine ] -1,1 ' -dibromide (concentration 2mM in aqueous sodium chloride solution at pH 7) at a scan rate of 20mV/s according to example 3 of the present invention;
FIG. 8 shows a flow battery comprising the compound of example 1 as a positive electrode and the compound of example 3 as a negative electrode according to the present invention at a charge/discharge rate of 10mA/cm2Lower coulombic and energy efficiency;
fig. 9 is a graph of the cycling stability of flow batteries composed of the compounds of examples 1 and 3 according to the present invention;
reference numerals:
an aqueous nano-polymer flow battery system 100;
an electrolyte reservoir 10;
a flow cell stack 20; a pole plate 21; the positive electrode electrolyte 22; the negative electrode electrolyte 23; a battery separator 24; a circulation line 25; a circulation pump 26; and a current collector 27.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the invention. Furthermore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
First, the dual-electron flow battery system 100 according to the embodiment of the present invention will be described in detail with reference to the drawings.
As shown in fig. 1, a dual-electron compound flow battery system 100 according to an embodiment of the present invention includes two electrolyte reservoirs 10 and a flow cell stack 20.
Specifically, the two electrolyte liquid storage banks 10 are oppositely arranged at intervals, the electrolyte liquid storage banks 10 are salt cavities with physical dissolving cavities formed after salt mines are mined, electrolyte is stored in the dissolving cavities, the electrolyte comprises a positive active material, a negative active material and a supporting electrolyte, and the positive active material is TEMPO-4-sodium sulfonate; the negative active material is an asymmetric double-electron viologen compound; the positive active material and the negative active material are directly dissolved or dispersed in a system using water as a solvent in a bulk form and are respectively stored in two salt cavities, the supporting electrolyte is dissolved in the system, and the flow battery stack 20 is respectively communicated with two electrolyte liquid storage reservoirs 10.
The flow battery stack 20 includes an electrolytic cell body, two electrode plates 21, a battery diaphragm 24, a current collector 27, a circulation pipeline 25 and a circulation pump 26. Specifically, the electrolytic cell body is filled with electrolyte, two pole plates are oppositely arranged, a cell diaphragm 24 is positioned in the electrolytic cell body, the cell diaphragm 24 divides the electrolytic cell body into a positive pole region communicated with one electrolyte reservoir 10 and a negative pole region communicated with the other electrolyte reservoir 10, one pole plate is arranged in the positive pole region, the other pole plate is arranged in the negative pole region, a positive electrolyte containing a positive active material is arranged in the positive pole region, a negative electrolyte containing a negative active material is arranged in the negative pole region, the cell diaphragm 24 can support the electrolyte to penetrate through and prevent the positive active material and the negative active material from penetrating through, a current collector 27 collects and conducts current generated by the active material of the flow cell stack 20, a circulation pipeline 25 inputs or outputs the electrolyte in one electrolyte reservoir 10 to the positive pole region, the circulation pipeline 25 inputs or outputs the electrolyte in the other electrolyte reservoir 10 to the negative pole region, the circulation pump 26 is provided in the circulation line 25, and the electrolyte is circulated and supplied by the circulation pump 26.
Specifically, the two electrolyte liquid reservoirs 10 are arranged oppositely at intervals, the electrolyte liquid reservoirs 10 are small storage tanks or salt cavities with physical containing cavities formed after salt mine mining, electrolyte is stored in the salt cavities, the electrolyte comprises a positive active material, a negative active material and a supporting electrolyte, and the positive active material is TEMPO-4-sodium sulfonate; the negative electrode active substance is an asymmetric double-electron viologen compound, the positive electrode active substance and the negative electrode active substance are directly dissolved or dispersed in a system taking water as a solvent in a body form and are respectively stored in two salt holes, a supporting electrolyte is dissolved in the system, the flow battery stack 20 is respectively communicated with two electrolyte liquid storage banks 10, the electrolyte is filled in the electrolytic cell body, two polar plates are oppositely arranged, a battery diaphragm 24 is positioned in the electrolytic cell body, the battery diaphragm 24 divides the electrolytic cell body into a positive electrode area communicated with one electrolyte liquid storage bank 10 and a negative electrode area communicated with the other electrolyte liquid storage bank 10, one polar plate is arranged in the positive electrode area, the other polar plate is arranged in the negative electrode area, the positive electrode area is internally provided with a positive electrode electrolyte 22 comprising the positive electrode active substance, the negative electrode area is internally provided with a negative electrolyte 23 comprising the negative electrode active substance, and the battery diaphragm 24 can be penetrated by the supporting electrolyte, the penetration of the positive active material and the negative active material is prevented, the electrolyte in one electrolyte liquid storage 10 is input or output to the positive region by the circulating pipeline 25, the electrolyte in the other electrolyte liquid storage 10 is input or output to the negative region by the circulating pipeline 25, the circulating pump 26 is arranged on the circulating pipeline 25, the electrolyte is circularly supplied by the circulating pump 26, and the current generated by the active material of the flow battery stack 20 is collected and conducted to an external lead by the two current collectors 27.
In other words, the dual-electron compound flow battery system according to the embodiment of the present invention includes two electrolyte solution reservoirs 10 and a flow battery stack 20, where the flow battery stack 20 includes two electrode plates, two current collectors 27, an electrolytic cell body, a battery diaphragm 24, a circulation pipeline 25, and a circulation pump 26, the electrolyte solution reservoir 10 is an underground cave, i.e., a salt cave, left after salt mine is mined in a water-soluble manner, and an electrolyte solution is stored in the salt cave, where the electrolyte solution includes a positive electrode active material, a negative electrode active material, and a supporting electrolyte, and the positive electrode active material is a TEMPO-4-sulfonic acid sodium salt; the negative active substance is an asymmetric double-electron viologen compound, the positive active substance and the negative active substance are dissolved or dispersed in a system taking water as a solvent in a body form, a supporting electrolyte is dissolved in the system, the flow battery stack 20 is respectively communicated with two electrolyte liquid storage reservoirs 10 through a circulating pipeline 25, two polar plates are oppositely arranged, a circulating pump 26 is arranged on the circulating pipeline 25, the electrolyte circularly flows to the polar plates through the circulating pump 26, the two polar plates can be respectively a positive plate and a negative plate, the polar plates are directly contacted with the electrolyte, an electrochemical reaction place with rich pore channels is provided, a battery diaphragm 24 is positioned in an electrolytic cell body, the battery diaphragm 24 can be penetrated by the supporting electrolyte to prevent the positive active substance and the negative active substance from penetrating, and the battery diaphragm 24 can be a cation exchange membrane.
Therefore, according to the dual-electron compound flow battery system 100 of the embodiment of the present invention, by using a device combining two electrolyte reservoirs 10 and a flow battery stack 20, the flow battery stack 20 uses a device combining two electrode plates 21, an electrolytic cell body, a battery diaphragm 24, a circulation pipeline 25, a circulation pump 26, and a current collector 27, and uses TEMPO-4-sulfonic acid sodium salt as a positive electrode active material, and an asymmetric dual-electron viologen compound as a negative electrode active material, the dual-electron compound flow battery system 100 can be applied to a battery environment of a salt cavity system (using an in-situ generated electrolyte), has the advantages of low cost, easy preparation of an active material, high safety performance, high energy density, stable charging and discharging performance, and high solubility of the active material, and can solve the problem of electrochemical energy storage in a large scale (megawatt/megawatt hour), fully utilizes some waste salt cavern (ore) resources.
Example 1
Synthesis of TEMPO-4-sulfonic acid sodium salt
5g (29.03mmol) of 4-OH-TEMPO and 20mL of dichloromethane solvent are added into a three-necked flask, after the 4-OH-TEMPO is dissolved, 2mL of chlorosulfonic acid is added dropwise with stirring at room temperature, and after the addition is finished, stirring is continued for 20 minutes at room temperature. After the reaction was completed, a saturated sodium bicarbonate solution was added dropwise to adjust the pH of the resulting reaction solution to 7, and the unreacted 4-OH-TEMPO was removed by extraction twice with ethyl acetate. And (3) decompressing and spin-drying the solvent to obtain a mixture containing TEMPO-4-sulfonic acid sodium salt and sodium sulfonate, extracting TEMPO-4-sulfonic acid sodium salt in the mixed solid by using absolute ethyl alcohol, decompressing and removing the solvent to obtain yellow solid. Nuclear magnetic characterization was not performed due to the presence of free radicals in the molecule.
Example 2
Synthesis of 1- (2-hydroxy-ethyl) - [4, 4' -bipyridine ] -1-onium bromide
Adding 3.436g (22mmol) of 4,4 '-bipyridine and 50mL of acetonitrile solvent into a three-necked bottle, adding 2.631g (20mmol 95%) of 2-bromoethanol after the 4, 4' -bipyridine is dissolved, heating to 90 ℃, refluxing and stirring for reaction, gradually generating off-white precipitate after 8h, and continuing to react for 40h until the reaction is complete. The resulting reaction solution was cooled and filtered with suction, washed 3 times, and finally dried under vacuum to give 5.628g of off-white powdery solid particles (named 1- (2-hydroxy-ethyl) - [4, 4' -bipyridine ] -1-phosphonium bromide, 91% yield).
Example 3
Synthesis of 1- (2-hydroxy-ethyl) -1 ' - (3-sulfo-propyl) - [4,4 ' -bipyridine ] -1,1 ' -dibromide
5.904g (21mmol) of 1- (2-hydroxy-ethyl) - [4, 4' -bipyridine ] -1-bromide, 2.467g (20mmol, 99%) of 1, 3-propane sultone and 50mL of acetonitrile solvent are added into a three-necked flask, the mixture is heated to 90 ℃ and stirred under reflux for reaction, after 4 hours, the off-white precipitate begins to become light yellow precipitate, and the reaction is continued for 20 hours until the reaction is completed. The resulting reaction solution was cooled and filtered, washed 3 times, and finally dried in vacuo to give 7.410g of pale yellow powdery solid particles (named 1- (2-hydroxy-ethyl) -1 ' - (3-sulfonic-propyl) - [4,4 ' -bipyridine ] -1,1 ' -onium bromide, yield 87.5%).
Electrochemical property test
(1) TEMPO-4-sodium sulfonate salt solutions (TEMPO-4-sodium sulfonate concentration 10mg/mL in 1M NaCl as supporting electrolyte) were studied by Cyclic Voltammetry (CV).
(2) 1- (2-hydroxy-ethyl) -1 '- (3-sulfo-propyl) - [4, 4' -bipyridine ] -1,1 '-dibromide solution (1- (2-hydroxy-ethyl) -1' - (3-sulfo-propyl) - [4,4 '-bipyridine ] -1, 1' -dibromide) was investigated by Cyclic Voltammetry (CV) at 5mg/mL in a solution of 1M NaCl as a supporting electrolyte, wherein the scanning rate was 0.5V/s.the CV curve of the compound in FIG. 7 shows its reduction peak at around-0.500V and its oxidation peak at around-0.420V.
(3) Using 100mA/cm2The current density of (a) was measured for the cycling performance of the flow battery system by charging and discharging the flow battery system, see fig. 8 and 9. FIG. 8 shows 25mA/cm2According to the curve of the charge capacity, the discharge capacity and the coulombic efficiency of the bi-electron compound flow battery which circulates for 200 times under the charge-discharge current density, the coulombic efficiency of molecules and the energy efficiency are basically kept unchanged, wherein the coulombic efficiency is stabilized to be more than 99%, and the energy efficiency is stabilized to be about 80%. The battery has smaller internal discharge phenomenon and higher energy utilization efficiency. FIG. 9 shows 25mA/cm2The charge-discharge capacity diagram of the bi-electron compound flow battery which is cycled for 200 times under the charge-discharge current density is consistent with the variation trend of coulombic efficiency and energy efficiency, and the utilization rate of the active material is about 70%.
According to the dual-electron compound flow battery system 100 of the embodiment of the invention, by adopting a device combining two electrolyte liquid storage reservoirs 10 and a flow battery stack 20, the flow battery stack 20 adopts a device combining two polar plates 21, an electrolytic cell body, a battery diaphragm 24, a circulation pipeline 25, a circulation pump 26 and a current collector 27, TEMPO-4-sodium sulfonate is adopted as a positive electrode active material, an asymmetric dual-electron viologen compound is adopted as a negative electrode active material, the dual-electron compound flow battery system 100 can be suitable for the battery environment of a salt cavity system (by using an in-situ generated electrolyte), has the advantages of low cost, easy preparation of an active material, high safety performance, high energy density, stable charging and discharging performance and high solubility of the active material, and can solve the problem of electrochemical energy storage in a large scale (megawatt/megawatt hour), fully utilizes some waste salt cavern (ore) resources.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (22)
1. The double-electron compound flow battery system based on the salt holes is characterized by comprising a positive electrode active material and a negative electrode active material, wherein TEMPO-4-sulfonic acid sodium salt is used as the positive electrode active material, an asymmetric double-electron viologen compound is used as the negative electrode active material, and the TEMPO-4-sulfonic acid sodium salt has a chemical structural formula as follows:
the chemical structural formula of the asymmetric two-electron viologen compound is as follows:
2. the two-electron compound flow battery system of claim 1, wherein the preparation of the TEMPO-4-sulfonic acid sodium salt comprises the steps of:
taking 4-hydroxy-2, 2,6, 6-tetramethyl piperidinyloxy (hereinafter referred to as 4-OH-TEMPO) containing positive active molecules as a raw material, sulfonating chlorosulfonic acid, and then neutralizing by sodium bicarbonate to directly prepare TEMPO-4-sulfonic acid sodium salt, wherein the chemical reaction formula is shown as a formula (1):
3. the synthesis method according to claim 2, characterized in that the preparation of the TEMPO-4-sulfonic acid sodium salt comprises the following specific steps:
dissolving 4-OH-TEMPO in dichloromethane, stirring at room temperature, dropwise adding chlorosulfonic acid, and stirring at room temperature for 5 minutes after the addition is finished. After the reaction is finished, adding a small amount of ice water into the reaction mixed solution to quench the reaction, then dropwise adding saturated sodium bicarbonate solution, adjusting the pH of the obtained reaction solution to 7, and then extracting twice with ethyl acetate to remove unreacted 4-OH-TEMPO. And (3) decompressing and spin-drying the solvent to obtain a mixture containing TEMPO-4-sulfonic acid sodium salt and sodium sulfonate, extracting TEMPO-4-sulfonic acid sodium salt in the mixed solid by using absolute ethyl alcohol, decompressing and removing the solvent to obtain yellow solid.
4. The synthesis method of claim 2, wherein the chlorosulfonic acid is used to replace the conventional sulfonation reagent concentrated sulfuric acid, the whole reaction can be completed in one step, 4-OH-TEMPO is not required to be fed in batches, the reaction steps are reduced, the consumption of the sulfonation reagent in the reaction is low, a large amount of alkaline solution is not required to be neutralized, a large amount of water is not required to be distilled in the post-treatment process, and the cost and energy consumption of the reaction are greatly reduced.
5. The bi-electron compound flow battery system according to claim 1, wherein the asymmetric bi-electron viologen compound is mainly made of 4,4 '-bipyridine through two different electrophilic substitutions, 4, 4' -bipyridine itself has no electrochemical activity, two N's at the 4 th position and the 4' th position are easy to be electrophilic substitutions, namely Menschutkin reaction, but common electrophilic substitution products such as methyl viologen can only be used as single electron energy storage material in an aqueous flow battery, the electrically neutral products are not dissolved in aqueous solution, by adopting a strategy of increasing the molecular hydrophilization of viologen, two hydrophilic groups of hydroxyl group and sulfonic group are respectively introduced at the two N's at the 4 th position and the 4' th position, not only the water solubility problem of the product is solved, but also the product has two electron gaining and losing ability, the electrochemical performance of the catalyst is better in a neutral aqueous phase system.
6. The two-electron compound flow battery system of claim 1, wherein the preparation of the asymmetric two-electron viologen compound comprises the steps of:
the method is characterized in that a self-synthesized mono-substituted viologen compound and 1, 3-propane sultone are used as raw materials, and an asymmetric two-electron viologen compound is prepared through a Menschutkin reaction, wherein the chemical reaction formula is shown as a formula (2):
wherein n represents the length of an alkyl chain and is one of 2-6.
7. The method of synthesis according to claim 6, further comprising the steps of:
mixing 4, 4-bipyridine containing negative active molecules and hydroxyl-terminated substituted alkyl bromide, adding the mixture into a reaction solution, and carrying out a Menschutkin reaction to obtain a mono-substituted viologen compound, wherein the chemical reaction formula is shown as formula (3):
8. the synthetic method according to claim 6, wherein the preparation of the asymmetric two-electron viologen compound comprises the following specific steps:
dissolving 4, 4' -bipyridine in an acetonitrile solvent, adding alkyl bromide substituted by hydroxyl, heating to 90 ℃, refluxing, stirring and reacting, stopping heating after the reaction is completed, cooling to room temperature, cooling the obtained reaction liquid, performing suction filtration, washing the solid for 3 times, and finally performing vacuum drying to obtain a mono-substituted viologen compound;
and (2) mixing the mono-substituted viologen compound prepared in the step and 1, 3-propane sultone, adding an acetonitrile solvent, heating to 90 ℃, refluxing and stirring for reaction, stopping heating after the reaction is completed, cooling to room temperature, cooling the obtained reaction liquid, performing suction filtration, washing the solid for 3 times, and finally performing vacuum drying to obtain the asymmetric two-electron viologen compound.
9. The dual-electron compound flow battery system of claim 1, further comprising: the electrolyte comprises two electrolyte liquid reservoirs, wherein the two electrolyte liquid reservoirs are arranged at intervals, each electrolyte liquid reservoir is a liquid storage tank for storing electrolyte or a salt cave which is formed after salt mine mining and is provided with a physical dissolution cavity, the electrolyte in one electrolyte liquid reservoir comprises the positive active substance and supporting electrolyte, the electrolyte in the other electrolyte liquid reservoir comprises the negative active substance and supporting electrolyte, and the positive active substance and the negative active substance are respectively directly dissolved or dispersed in a system taking water as a solvent in a bulk form;
the flow battery stack comprises a battery diaphragm, the battery diaphragm divides the flow battery stack into an anode area and a cathode area which are distributed at intervals, the anode area is communicated with one electrolyte liquid storage tank, and the cathode area is communicated with the other electrolyte liquid storage tank.
10. The bi-electronic compound flow battery system of claim 9, wherein the concentration of the positive electrode active material is 0.2 mol-L-1～6.0mol·L-1The concentration of the negative electrode active material is 0.1 mol.L-1～3.0mol·L -1。
11. The bi-electronic compound flow battery system of claim 10, wherein the electrolyte reservoir is a pressurized sealed container with a pressure of 0.1MPa to 0.5 MPa.
12. The bi-electronic compound flow battery system of claim 9, wherein an inert gas is introduced into the electrolyte reservoir to purge and maintain pressure.
13. The dual-electron compound flow battery system of claim 12, wherein the inert gas is nitrogen or argon.
14. The bi-electronic compound flow battery system of claim 9, wherein the battery diaphragm is an anion exchange membrane, a cation exchange membrane or a polymer porous membrane with a pore size of 10nm to 300 nm.
15. The bi-electronic compound flow battery system of claim 9, wherein the supporting electrolyte is a NaCl salt solution, a KCl salt solution, Na2SO4Salt solution, K2SO4Salt solution, MgCl2Salt solution, MgSO4Salt solution, CaCl2Salt solution, NH4At least one of a Cl salt solution.
16. The bi-electronic compound flow battery system of claim 15, wherein the molar concentration of the supporting electrolyte is 0.1 mol-L-1～8.0mol·L-1。
17. The bi-electronic compound flow battery system of claim 9, wherein the anode region and the cathode region are each provided with an electrode therein, and the positive and negative electrodes are carbon material electrodes.
18. The two-electron compound flow battery system of claim 17, wherein the carbon material electrode is one or more of carbon felt, carbon paper, carbon cloth, carbon black, activated carbon fiber, activated carbon particles, graphene, graphite felt, and a glassy carbon material.
19. The bi-electronic compound flow battery system of claim 18, wherein the electrodes are formed as electrode plates having a thickness of 2mm to 8 mm.
20. The dual-electron compound flow battery system of claim 9, further comprising: and the current collectors are respectively arranged on two sides of the flow battery stack and can collect and conduct current generated by active substances of the flow battery stack to an external lead.
21. The bi-electronic compound flow battery system of claim 20, wherein the current collector is one of a conductive metal plate, a graphite plate, or a carbon-plastic composite plate.
22. The bi-electronic compound flow battery system of claim 21, wherein the conductive metal plate comprises at least one metal of copper, nickel, aluminum.
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