CN115894350A - Steric-hindrance-protected single-electron bipyridine derivative and application thereof in flow battery - Google Patents

Steric-hindrance-protected single-electron bipyridine derivative and application thereof in flow battery Download PDF

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CN115894350A
CN115894350A CN202211284870.7A CN202211284870A CN115894350A CN 115894350 A CN115894350 A CN 115894350A CN 202211284870 A CN202211284870 A CN 202211284870A CN 115894350 A CN115894350 A CN 115894350A
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flow battery
electrolyte
bipyridine
bpy
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徐俊辉
赵宇
刘跃
陈留平
姚圣鑫
王慧
李悦
武奕
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Hangzhou Normal University
China Salt Jintan Co Ltd
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Abstract

The invention relates to the field of negative electrode materials of flow batteries, in particular to a single-electron bipyridyl derivative protected by steric hindrance and application thereof in a flow battery. The electrochemically stable 2,2 '-alkoxy-4, 4' -bipyridine (Bpy-OR) serving as the flow battery organic negative electrode material has a lower oxidation-reduction potential, and can improve the voltage and the cycle life of the organic flow battery. Bpy-OR adopts a steric hindrance protection strategy, through introducing an alkoxy functional group on the 2-position of two pyridine rings of 4,4' -bipyridyl, the steric hindrance of the functional group is utilized to prevent the active material from generating side reactions (mainly dimerization reaction and nucleophilic reaction to nitrogen atoms) in the oxidation reduction process, and in addition, the introduced alkoxy functional group is an electron-withdrawing group, so that the reduction potential can be further reduced, and the voltage of the battery can be increased.

Description

Steric-hindrance-protected single-electron bipyridine derivative and application thereof in flow battery
Technical Field
The invention relates to the field of negative electrode materials of flow batteries, in particular to a steric-hindrance protection one-electron bipyridyl derivative and application thereof in a flow battery.
Background
The redox flow battery is an energy storage system with high cycle efficiency, adjustable properties and wide prospect. Compared with an inorganic flow battery system, the organic flow battery using organic molecules as redox active materials has the advantages of low cost, high voltage, good reversibility, adjustable structure and the like.
4,4' -bipyridine and derivatives thereof are used as typical negative active materials of organic flow batteries, and have attracted research interest due to their diverse structures and simple chemical modifications. The most common 4,4' -bipyridine derivative is methyl viologen, which can be synthesized by reacting bipyridine with methyl iodide, and has high reaction yield and large-scale production. When methyl viologen is used in combination with 4-hydroxy-2, 6-tetramethylpiperidine-1-oxyl, the battery capacity is 13.40Ah L -1 The 24h capacity loss was 3.6%, this high capacity loss being due to dimerization of the intermediate viologen cation. In order to prevent dimerization, the capacity loss rate of the battery was reduced to 0.03% by introducing a quaternary ammonium salt group into viologen by coulomb repulsion. In addition, sulfonated functionalized viologens also have similar effects.
Although 4,4' -bipyridine and derivatives thereof have made great progress in the development and research in the field of long-cycle-life aqueous organic flow batteries, there are few reports on non-aqueous flow batteries. Although the bipyridyl series material has relatively negative oxidation-reduction potential (-1.8V vs. Ag/AgCl) in an organic solvent, the application of the bipyridyl series material in the aspect of battery electrodes is not deeply researched. In addition, although partially negative potential nonaqueous phase anode materials (quinones and azos) have been reported, they all have disadvantages of high redox potential, short cycle life, and the like.
Disclosure of Invention
The invention aims to provide an organic cathode material of a flow battery, which is simple and convenient to synthesize, has lower oxidation-reduction potential and stable electrochemistry, and improves the voltage and the cycle life of the organic flow battery.
The bipyridyl-based organic molecular flow battery cathode material 2,2 '-alkoxy-4, 4' -bipyridyl (Bpy-OR) designed based on a steric hindrance protection strategy has the following structural general formula:
Figure BDA0003899361070000021
wherein R = Me, et, iPr, tBu.
When R = Me in the structure, the structure of 2,2 '-methoxy-4, 4' -bipyridine (Bpy-OMe) is as follows:
Figure BDA0003899361070000022
the invention also provides a preparation method of Bpy-OMe, which utilizes the catalytic coupling reaction of zinc powder and nickel triphenylphosphine dibromide as catalysts to prepare Bpy-OMe, and comprises the following specific synthesis steps:
weighing zinc powder, nickel triphenylphosphine dibromide and tetraethylammonium iodide, sequentially adding the zinc powder, the nickel triphenylphosphine dibromide and the tetraethylammonium iodide into a 250mL two-neck round-bottom flask, exhausting gas for 3 times to remove oxygen in the flask, injecting tetrahydrofuran under the protection of nitrogen, stirring for 30 minutes, then injecting a tetrahydrofuran solution dissolved with 2-alkoxy-4-bromopyridine under the protection of nitrogen, heating and stirring for 2 hours at 50 ℃, after the reaction is finished, cooling the mixture to room temperature, pouring the mixture into ammonia water, adding chloroform for extraction, filtering the mixed solution to remove solid impurities, and keeping the filtrate; taking the lower organic liquid after the filtrate is layered, and extracting the upper aqueous solution with chloroform for 2 times; combining the organic liquids, washing with saturated salt water for 3 times, drying with anhydrous sodium sulfate, and removing the solvent by vacuum rotary evaporation to obtain a crude product; finally, the white solid powder product is obtained by column chromatography extraction, namely the 2,2 '-alkoxy-4, 4' -bipyridyl.
The invention also provides a method for applying the Bpy-OR as a negative electrode active material in an organic flow battery, which comprises the following specific contents:
preparing a negative electrode electrolyte based on a Bpy-OR active material: weighing quantitative negative active material Bpy-OR, adding into conventional electrolyte to prepare solution with concentration of 0.05-1.0M as negative electrolyte.
The conventional electrolyte comprises an organic solvent and an electrolyte salt, wherein the organic solvent is preferably but not limited to an acetonitrile solvent, the electrolyte salt is preferably but not limited to tetrabutylammonium hexafluorophosphate, and the concentration of the electrolyte salt is preferably but not limited to 1.0M.
Preparing a positive electrolyte: and weighing a certain amount of positive electrode active material, adding the positive electrode active material into the conventional electrolyte to prepare a solution with the same concentration as that of the negative electrode electrolyte, namely the positive electrode electrolyte.
The positive active material includes, but is not limited to, organic molecules having a high redox potential and a high solubility in an organic solvent, such as ferrocene.
Assembling and testing a flow battery: the battery system comprises positive and negative end plates, positive and negative current collectors, a porous diaphragm and positive and negative liquid storage tanks, wherein the positive and negative liquid storage tanks are filled with electrolyte (positive and negative electrolyte). And respectively filling positive electrolyte and negative electrolyte into positive and negative liquid storage tanks by using a liquid transfer gun in a glove box filled with nitrogen, sealing the battery, and testing the electrochemical performance of the battery on a battery testing system.
The diaphragm is a thin film with high ion conductivity, and comprises Daramic AA-800, PP film and the like.
Current collectors include, but are not limited to, graphite carbon felt, conductive carbon layers, and the like.
Advantageous effects
By adopting a steric hindrance protection strategy, alkoxy functional groups are introduced on the 2 nd positions of two pyridine rings of 4,4' -bipyridyl, the steric hindrance of the functional groups is utilized to prevent the active material from generating side reactions (mainly dimerization reaction and nucleophilic reaction to nitrogen atoms) in the oxidation-reduction process, and in addition, the introduced alkoxy functional groups are electron-withdrawing groups, so that the reduction potential can be further reduced, and the voltage of the battery can be increased. Furthermore, through molecular structure design, the organic anode material with overall excellent electrochemical performance is designed by comprehensively considering the steric hindrance protection effect, the pi-pi interaction of the organic molecule, the energy levels of the lowest unoccupied orbital (LUMO) and the highest occupied orbital (HOMO) of the organic molecule and the like.
Description of the drawings:
the invention will be further elucidated by means of exemplary embodiments, which will be described in detail by means of the drawing. These embodiments are not intended to be limiting, and in these embodiments like numerals are used to indicate like structures, wherein:
FIG. 1 is the electrostatic potential (ESP) of 4,4' -bipyridine and 2,2' -methoxy-4, 4' -bipyridine (Bpy-OMe).
FIG. 2 is a graph of the HOMO-LUMO energy levels of 4,4' -bipyridine and 2,2' -methoxy-4, 4' -bipyridine (Bpy-OMe).
FIG. 3 is the interaction energy and distance between different valence states of 4,4' -bipyridine (Bp) and 2,2' -methoxy-4, 4' -bipyridine (MeOBP).
FIG. 4 a scheme for the synthesis of Bpy-OMe.
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of Bpy-OMe.
FIG. 6 is a plot of cyclic voltammograms of 2,2' -methoxy-4, 4' -bipyridine (Bpy-OMe) and 4,4' -bipyridine (Bpy).
FIG. 7 is a plot of cyclic voltammograms of Bpy-OMe cycling through 100 cycles.
FIG. 8 is a graph of the cycling charge-discharge capacity and efficiency of a 2,2 '-methoxy-4, 4' -bipyridine (Bpy-OMe) | ferrocene flow battery.
FIG. 9 is a graph of capacity versus voltage for a 2,2 '-methoxy-4, 4' -bipyridine (Bpy-OMe) | ferrocene flow battery.
Fig. 10 is a graph of the cycling charge-discharge capacity and efficiency of a 4,4' -bipyridine (Bpy) | ferrocene flow battery.
Fig. 11 is a graph of capacity versus voltage for a 4,4' -bipyridyl (Bpy) | ferrocene flow battery.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention and is provided in the context of a particular application and its requirements. Various modifications to the disclosed embodiments will be apparent to those skilled in the art. In addition, the general principles defined in this disclosure may be applied to other embodiments and applications without departing from the spirit and scope of the present disclosure. Therefore, the present invention is not limited to the disclosed embodiments, but is to be accorded the widest scope consistent with the claims.
Example 1,2 '-methoxy-4, 4' -bipyridine (Bpy-OMe) synthesis and flow battery applications thereof
The synthetic route of 2,2 '-methoxy-4, 4' -bipyridine (Bpy-OMe) is shown in FIG. 4, and specifically comprises the following steps: 0.49g (7.50 mmol) of zinc powder, 1.12g (1.50 mmol) of triphenylphosphine nickel dibromide and 1.29g (1.5 mmol) of tetraethylammonium iodide were weighed out and added to a 250mL two-necked round-bottomed flask in this order, the flask was purged 3 times to remove oxygen, 15mL of Tetrahydrofuran (THF) was charged under nitrogen, and after stirring for 30 minutes, a tetrahydrofuran solution containing 0.93g (5 mmol) of 2-methoxy-4-bromopyridine was charged under nitrogen, and the mixture was heated and stirred at 50 ℃ for 2 hours. After the reaction is finished, cooling the mixture to room temperature, pouring the mixture into 30mL of 2M ammonia water, adding 100mL of chloroform for extraction, filtering the mixed solution to remove solid impurities, and keeping the filtrate; taking the lower layer of organic liquid after the filtrate is layered, and extracting the upper layer of aqueous solution with 50mL of chloroform for 2 times; combining the organic liquids, washing the organic liquids with saturated salt water for 3 times, drying the organic liquids with anhydrous sodium sulfate, and removing the solvent by vacuum rotary evaporation to obtain a crude product; and finally purifying by column chromatography to obtain a white solid powdery product, namely Bpy-OMe.
FIG. 5 is a NMR spectrum of Bpy-OMe, which demonstrates the successful synthesis of Bpy-OMe.
Compared with 4,4' -bipyridyl, after methoxy is introduced as a functional group, the area of the more negative electrostatic potential energy surface around the N atom of the active site on the pyridine ring of 2,2' -methoxy-4, 4' -bipyridyl (Bpy-OMe) is reduced and is surrounded by the more positive red electrostatic potential energy surface of methoxy, which shows that due to the steric protection effect of methoxy, the attack of side reactions initiated by material molecules in the redox process can be effectively reduced, so that the stability of the redox intermediate is improved, and the cycle stability of the redox intermediate is improved. As shown in FIG. 1, the electrostatic potentials (ESP) of 4,4' -bipyridine and 2,2' -methoxy-4, 4' -bipyridine (Bpy-OMe) are shown.
2,2' -methoxy-4, 4' -bipyridine (Bpy-OMe) had a LUMO level 0.23V higher than that of 4,4' -bipyridine. The energy level diagrams of the lowest unoccupied orbital (LUMO) and the highest occupied orbital (HOMO) of 4,4' -bipyridine and 2,2' -methoxy-4, 4' -bipyridine are shown in FIG. 2.
The pi-pi interaction of organic molecules has a larger effect on the electrochemical application of the molecules, so that on one hand, the distance between the molecules is reduced, the solubility of the material is reduced, and the cycle stability of the battery is influenced; on the other hand, certain pi-pi interaction can average the charge distribution on the reduced N atom of the bipyridyl material, thereby improving the stability of the reduced free radical molecule. A certain pi-pi interaction exists in three molecular structures of 2,2 '-methoxy-4, 4' -bipyridine (Bpy-OMe) with different valence states, and the interaction energy is also larger than the value between the 4,4 '-bipyridine and the molecules of 4,4' -biquinoline with different valence states. FIG. 3 is the interaction energy and distance between different valence states of 4,4' -bipyridine (Bp) and 2,2' -methoxy-4, 4' -bipyridine (MeOBP). In addition, the pi-pi interaction isosurface area tends to increase and then decrease with the increase of the reduced molecules, wherein the neutral and reduced 2,2 '-methoxy-4, 4' -bipyridine (MeOBP-MeOBP) are - ) The pi-pi interaction between them is maximal. As shown in fig. 3.
Flow battery applications of 2,2 '-methoxy-4, 4' -bipyridine (Bpy-OMe):
preparing a cathode electrolyte based on a Bpy-OMe active material: the negative electrode active material Bpy-OMe was weighed and added to a conventional electrolyte to prepare a negative electrode electrolyte having a concentration of 0.20M.
Preparing a positive electrode electrolyte: and weighing the positive electrode active material, and adding the positive electrode active material into a conventional electrolyte to prepare a positive electrode electrolyte with the concentration of 0.20M.
Assembling and testing a flow battery: the battery system comprises positive and negative end plates, positive and negative current collectors, a porous diaphragm and positive and negative liquid storage tanks, wherein the positive and negative liquid storage tanks are filled with the positive and negative electrolyte. And respectively filling positive electrolyte and negative electrolyte into positive and negative liquid storage tanks by using a liquid transfer gun in a glove box filled with nitrogen, sealing the battery, and testing the electrochemical performance of the battery on a battery testing system.
The electrochemical performance of the Bpy-OMe | ferrocene flow battery is tested by Cyclic Voltammetry (CV), 2 '-methoxy-4, 4' -bipyridine has good electrochemical reversibility, and the reduction potential in an electrolyte using acetonitrile as a solvent is-1.89V (vs. Ag/AgCl). Ferrocene (potential: 0.51V vs. Ag/AgCl) is selected as the matched anode material, the battery voltage can reach 2.4V, and 200 circles of stability can be kept in the battery cycle test, as shown in fig. 7 and 8.
FIG. 6 is a plot of cyclic voltammograms of 2,2' -methoxy-4, 4' -bipyridine (Bpy-OMe) and 4,4' -bipyridine (Bpy). The methoxy group is introduced into the 4,4' -bipyridine (Bpy) to reduce the oxidation-reduction potential of the material and make the potential more negative, so that the material can be used as a negative electrode material to be matched with a positive electrode material to obtain higher charge-discharge voltage.
FIG. 8 is a graph of the cycling charge and discharge capacity and efficiency of a 2,2 '-methoxy-4, 4' -bipyridine (Bpy-OMe) | ferrocene flow battery.
FIG. 9 is a graph of capacity versus voltage for a 2,2 '-methoxy-4,4' -bipyridine (Bpy-OMe) | ferrocene flow battery. According to the data, the discharge capacity of the first ring of the 2,2 '-methoxy-4, 4' -bipyridine | ferrocene flow battery is 2.51Ah/L, which is 46.8% of the theoretical capacity. After 200 cycles of charge and discharge, the discharge voltage of the battery is 2.20V, the coulombic efficiency of the battery is kept at 95%, and the energy efficiency is kept at 85%. The discharge capacity at the 200 th cycle was 2.06Ah/L, the capacity retention rate was 82%, and the rate of attenuation per cycle was 0.09%.
Example 2,2 '-methoxy-4, 4' -bipyridine (Bpy-OMe) synthesis and flow battery application 2,2 '-methoxy-4, 4' -bipyridine (Bpy-OMe) was synthesized according to the method and procedure of example 1.
Flow battery applications of 2,2 '-methoxy-4, 4' -bipyridine (Bpy-OMe):
preparing a cathode electrolyte based on a Bpy-OMe active material: the negative electrode active material Bpy-OMe was weighed and added to a conventional electrolyte to prepare a negative electrode electrolyte having a concentration of 0.30M.
Preparing a positive electrolyte: and weighing the positive electrode active material, and adding the positive electrode active material into a conventional electrolyte to prepare a positive electrode electrolyte with the concentration of 0.30M.
Assembling and testing a flow battery: the battery system comprises a positive electrode end plate, a negative electrode current collector, a porous diaphragm and a positive electrode liquid storage tank, wherein the positive electrode liquid storage tank and the negative electrode liquid storage tank are filled with electrolyte (positive electrode electrolyte and negative electrode electrolyte). And respectively filling positive electrolyte and negative electrolyte into positive and negative liquid storage tanks by using a liquid transfer gun in a glove box filled with nitrogen, sealing the battery, and testing the electrochemical performance of the battery on a battery testing system.
Example 3,2,2 '-methoxy-4, 4' -bipyridine (Bpy-OEt) synthesis and flow battery applications thereof
The synthesis of 2,2 '-ethoxy-4, 4' -bipyridine (Bpy-OEt) comprises the following specific steps:
0.49g (7.50 mmol) of zinc powder, 1.12g (1.50 mmol) of triphenylphosphine nickel dibromide and 1.29g (1.5 mmol) of tetraethylammonium iodide were weighed out and added to a 250mL two-necked round-bottomed flask, followed by 3 times degassing to remove oxygen in the flask, 15mL of Tetrahydrofuran (THF) was charged under nitrogen, and after stirring for 30 minutes, a tetrahydrofuran solution containing 1.01g (5 mmol) of 4-bromo-2-ethoxypyridine was charged under nitrogen, and the mixture was heated and stirred at 50 ℃ for 2 hours. After the reaction is finished, cooling the mixture to room temperature, pouring the mixture into 30mL of 2M ammonia water, adding 100mL of chloroform for extraction, filtering the mixed solution to remove solid impurities, and keeping the filtrate; taking the lower layer of organic liquid after the filtrate is layered, and extracting the upper layer of aqueous solution with 50mL of chloroform for 2 times; combining the organic liquids, washing the organic liquids with saturated salt water for 3 times, drying the organic liquids with anhydrous sodium sulfate, and removing the solvent by vacuum rotary evaporation to obtain a crude product; and finally purifying by column chromatography to obtain a white solid powdery product, namely Bpy-OEt.
Comparative example 1, 4' -bipyridine (Bpy) in a flow battery
Preparing a cathode electrolyte based on a Bpy active material: the negative electrode active material Bpy was weighed and added to a conventional electrolyte to prepare a negative electrode electrolyte having a concentration of 0.20M.
Preparing a positive electrolyte: and weighing the positive electrode active material, and adding the positive electrode active material into a conventional electrolyte to prepare a positive electrode electrolyte with the concentration of 0.20M.
Assembling and testing a flow battery: the battery system comprises positive and negative end plates, positive and negative current collectors, a porous diaphragm and positive and negative liquid storage tanks, wherein the positive and negative liquid storage tanks are filled with electrolyte (positive and negative electrolyte). And respectively filling positive electrolyte and negative electrolyte into positive and negative liquid storage tanks by using a liquid transfer gun in a glove box filled with nitrogen, sealing the battery, and testing the electrochemical performance of the battery on a battery testing system.
Fig. 10 is a graph of the cycling charge-discharge capacity and efficiency of a 4,4' -bipyridine (Bpy) | ferrocene flow battery.
Fig. 11 is a graph of capacity versus voltage for a 4,4' -bipyridine (Bpy) | ferrocene flow battery.
The first-circle discharge capacity of the 4,4' -bipyridyl | ferrocene static flow battery is 4.50Ah L -1 The theoretical capacity is 84%, after 200 cycles of charge and discharge, the discharge voltage of the battery is 1.75V, the coulombic efficiency of the battery is kept at 95%, the energy efficiency is kept at 50%, the discharge capacity at the 200 th cycle is 0.23Ah L-1, the capacity retention rate is only 5.11%, and the capacity decay rate per cycle is 0.47%, which shows that 4,4' -bipyridyl has fast capacity decay and low stability in actual battery tests.
Compared with the embodiment 1, the battery voltage is higher after the methoxyl group is introduced into the 2,2' -methoxyl-4, 4' -bipyridyl (Bpy-OMe) compared with the 4,4' -bipyridyl (Bpy) before the functional group is introduced, and the stability of the active material is improved due to the steric protection effect of the methoxyl group, so that the cycling stability of the battery is obviously improved.
The conventional electrolyte described in example 1, example 2, comparative example 1 was a 1M solution of tetrabutylammonium hexafluorophosphate in acetonitrile; the positive active material is ferrocene; the diaphragm is Daramic AA-800; the current collector is a graphite carbon felt.

Claims (8)

1. A steric-hindrance protection single-electron bipyridyl derivative is characterized in that the bipyridyl derivative is 2,2 '-alkoxy-4, 4' -bipyridyl (Bpy-OR), and the structural general formula of the bipyridyl derivative is as follows:
Figure FDA0003899361060000011
wherein R = Me, et, iPr, tBu.
2. The sterically hindered protected one-electron bipyridine derivative according to claim 1, wherein the bipyridine derivative is prepared by a method comprising: weighing zinc powder, nickel triphenylphosphine dibromide and tetraethylammonium iodide, sequentially adding the zinc powder, the nickel triphenylphosphine dibromide and the tetraethylammonium iodide into a two-neck round-bottom flask, pumping gas for 3 times to remove oxygen in the flask, injecting tetrahydrofuran under the protection of nitrogen, stirring for 30 minutes, then injecting a tetrahydrofuran solution dissolved with 2-alkoxy-4-bromopyridine under the protection of nitrogen, heating and stirring for 2 hours at 50 ℃, after the reaction is finished, cooling the mixture to room temperature, pouring the mixture into ammonia water, adding chloroform for extraction, filtering the mixed solution to remove solid impurities, and keeping the filtrate; taking the lower organic liquid after the filtrate is layered, and extracting the upper aqueous solution with chloroform for 2 times; after the organic liquids are combined, the mixture is washed for 3 times by saturated saline solution, dried by anhydrous sodium sulfate and subjected to vacuum rotary evaporation to remove the solvent, so that a crude product is obtained; finally, the white solid powder product is obtained by column chromatography extraction, namely the 2,2 '-alkoxy-4, 4' -bipyridyl.
3. The sterically hindered protected one-electron bipyridine derivative according to claim 2, wherein the alkoxy group includes but is not limited to methoxy (CH) 3 O-), ethoxy (C) 2 H 5 O-), propoxy (C) 3 H 7 O-)。
4. The sterically hindered protected one-electron bipyridine derivative according to claim 1, wherein the bipyridine derivative is 2,2'-methoxy-4, 4' -bipyridine (Bpy-OMe) having the structure:
Figure FDA0003899361060000012
5. the organic flow battery is characterized by comprising a positive electrode end plate, a negative electrode current collector, a porous diaphragm and a positive electrode liquid storage tank, wherein the positive electrode liquid storage tank and the negative electrode liquid storage tank are filled with electrolyte.
6. The organic flow battery of claim 5, wherein the organic flow battery negative electrolyte is: the negative electrode active material bipyridine derivative according to claim 1 is added to a conventional electrolyte to prepare a solution having a concentration of 0.05M to 1.0M, which is a negative electrode electrolyte.
7. The organic flow battery as claimed in claim 5, wherein the positive electrolyte of the organic flow battery is: adding the anode active material into the conventional electrolyte to prepare a solution with the concentration of 0.05-1.0M, namely the anode electrolyte; the positive active material includes, but is not limited to, ferrocene.
8. The organic flow battery of claim 5, wherein the method of assembling the flow battery is: and respectively filling positive and negative electrolytes into positive and negative liquid storage tanks by using a liquid transfer gun in the glove box filled with nitrogen, and sealing the flow battery system.
CN202211284870.7A 2022-10-20 2022-10-20 Steric-hindrance-protected single-electron bipyridine derivative and application thereof in flow battery Pending CN115894350A (en)

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