Multi-electron transfer quinone derivative as well as preparation method and application thereof

Abstract

The invention discloses a multi-electron transfer quinone derivative as well as a preparation method and application thereof. The multi-electron transfer quinone derivative has a structure as shown in a formula I, the multi-electron transfer quinone derivative takes a series of pyrene as a substrate, carbonyl redox centers are introduced to 4, 5, 9 and 10 sites through a low-cost metal catalytic oxidation reaction, then hydrophilic through a sulfonation reaction and used as a reversible couple, and the multi-electron transfer quinone derivative can be directly used as an electrolyte for an aqueous organic flow battery after being dissolved in water without subsequent treatment. The pyrene tetraketone derivative couple can realize two-to-four-step four-electron transfer in the oxidation-reduction process, and compared with a traditional organic active couple with single electron transfer, the volume capacity is improved by four times; meanwhile, due to the expanded conjugated structure of the pyrene tetraketone parent nucleus, the electron delocalization range is enlarged, and the rigidity of an organic framework is enhanced, so that the couple has excellent redox kinetics and cycling stability.

Description

Technical Field

[0001] This application relates to a multi-electron-transfer quinone derivative, its preparation method, and its application, belonging to the field of flow batteries. Background Technology

[0002] New energy sources will become the mainstay of electricity supply, but their intermittent and uncontrollable nature leads to a significant waste of renewable energy output. Developing energy storage technology is crucial for promoting the practicality of new energy sources. Among them, flow batteries, with their long cycle life and intrinsic safety, are particularly suitable for large-scale energy storage. However, the energy density of current flow batteries is generally low, and they mainly rely on inorganic metals as active redox couples. Factors such as limited reserves and distribution have led to their ever-increasing prices and relatively high system costs. Inorganic non-metallic halogen-based flow batteries, such as those based on iodine and bromine, also face challenges such as difficulty in performance control and severe shuttle effects, limiting their application scope.

[0003] Aqueous organic flow batteries utilize water-soluble organic molecules as electrochemical active materials, primarily composed of elements such as carbon, hydrogen, oxygen, and nitrogen, thus avoiding resource constraints. Existing technologies modify or polymerize pyrene-4,5,9,10-one molecules to reduce molecular polarity and use them as electrode materials, aiming to decrease their solubility in the electrolyte and alleviate capacity decay and limited cycle life caused by the dissolution and detachment of organic electrode materials from the electrode in static systems such as lithium-ion, sodium-ion, and aqueous zinc-ion batteries. However, this approach cannot completely eliminate dissolution, resulting in poor practical application performance and failing to solve the capacity decay problem. Furthermore, the low conductivity of pyrene-4,5,9,10-tetraketones leads to low content of positive electrode active material and low areal capacity when used as a positive electrode material, further limiting the battery's capacity and energy density. Adjusting the solubility, redox potential, and stability of organic active molecules through molecular engineering modification and electrolyte regulation becomes a feasible approach. Many organic reactive molecules have been reported, but most suffer from low actual energy density due to issues such as low solubility, low electrode potential, and low utilization of two electrons. Furthermore, their poor electrochemical stability and the need for inert gas protection significantly limit their practical applications. Therefore, there is an urgent need to develop more organic reactive molecules with high energy density and high stability. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention aims to provide a method for preparing multi-electron-transfer quinone derivatives and their application in high-energy-density flow battery systems by utilizing the multiple active sites of quinone derivatives. Using pyrene as a substrate, carbonyl redox centers are introduced at positions 4, 5, 9, and 10 through a low-cost metal-catalyzed oxidation reaction, followed by hydrophilic sulfonation to form a reversible redox couple. After dissolving in an aqueous solution, it can be directly used as an electrolyte in aqueous organic flow batteries without further treatment.

[0005] Compared to directly using pyrene-4,5,9,10-one as an electrode material, this invention modifies the pyrene-4,5,9,10-one redox couple, making it dissolve in the electrolyte for use in flow batteries. This alters the reaction mode and pathway of the redox couple, and the circulating flow of the pump ensures stable electron gain and loss on the electrode, thereby guaranteeing cycle stability. Furthermore, this invention hydrophilically modifies the redox couple, dissolving it in aqueous solution. Its capacity depends on its solubility rather than the loading of active molecules on the electrode, thus alleviating the problem of low conductivity of organic molecules and improving capacity and energy density.

[0006] Simultaneously, this redox couple enables four-electron transfer during redox processes, resulting in a fourfold increase in volumetric capacity compared to traditional organic active redox couples used in organic flow batteries for single-electron transfer. Furthermore, the extended conjugated structure of the pyrene tetraketone core enhances electron delocalization and strengthens the organic framework, thus providing the redox couple with both excellent redox kinetics and cycling stability. Moreover, the introduction of hydrophilic and electron-withdrawing sulfonic acid groups increases the solubility of the core and electrode potential, allowing for an operational concentration exceeding 1 M. The resulting flow battery with a vanadium anode exhibits an open-circuit voltage of ~1 V and a volumetric capacity exceeding 90 Ah / L. -1 Simultaneously, it exhibits stable cycling in air for up to 60 days with no capacity decay, while also improving kinetics at 80 mA cm⁻¹. -2 The energy efficiency is ~70% at this current density. Flow batteries assembled using this redox couple with electrolyte exhibit advantages such as low cost, high energy density, ultra-long cycle life, and high battery efficiency, showing great promise for large-scale energy storage applications.

[0007] According to a first aspect of this application, a multi-electron-transfer quinone derivative is provided, the multi-electron-transfer quinone derivative having the structure shown in Formula I:

[0008]

[0009] In Formula I, R1, R2, R3, R4, R5, and R6 are independently selected from -H, -OH, -F, -Cl, -Br, -CN, -NH2, -N(CH3)2, and -N(CH3)3. + One of the following: -OH, -SH, -OCH3, -SiH3, -CHO, -CF3, -COOH, -COOCH3, -CONH2, -NO2, -PO3H2, -SO3H, and C1 to C5 alkyl groups.

[0010] Optionally, at least one of R1, R2, R3, R4, R5, and R6 has a structure of -SO3H.

[0011] According to a second aspect of this application, a method for preparing the above-described multi-electron-transfer quinone derivative is provided, the method comprising the following steps:

[0012] (1) Mixture I containing pyrene compounds, catalyst, oxidant and solvent is reacted to obtain pyrene tetraketone precursors;

[0013] (2) A mixture containing a pyrene tetraketone precursor and fuming sulfuric acid is reacted in reaction II to obtain the multi-electron transfer quinone derivative.

[0014] Optionally, the pyrene compound is selected from at least one of pyrene, 1-bromo-pyrene, 1,6-bromo-pyrene, 1-hydroxypyrene, 1-carboxypyrene, 1-methanolpyrene, 1-formatepyrene, 1-butyratepyrene, and 1-pyrene-BETA-D-glucuronic acid.

[0015] Optionally, the catalyst is selected from at least one of ruthenium trichloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tris(dibenzylideneacetone)dipalladium(O), and palladium acetate.

[0016] Optionally, the oxidant is selected from at least one of sodium periodate, potassium permanganate, potassium dichromate, cerium tetroxide, periodic acid, potassium periodate, and calcium periodate.

[0017] Optionally, the solvent is selected from at least one of dichloromethane, acetonitrile, water, toluene, dimethyl sulfoxide, dimethylformamide, ethanol, and methanol.

[0018] Optionally, in step (1), the molar ratio of the pyrene compound to the catalyst is 100 to 1000:1.

[0019] Optionally, the molar ratio of the pyrene compound to the oxidant is 4 to 6:1.

[0020] Optionally, the amount of the pyrene compound and the solvent used is 40 to 400 g / L.

[0021] Optionally, in step (1), the temperature of reaction I is 0 to 100°C, and the reaction time is 2 to 24 hours.

[0022] Optionally, in step (2), the molar ratio of the pyrene tetraketone precursor to the fuming sulfuric acid is 1 to 4:1.

[0023] Optionally, in step (2), the temperature of reaction II is 0 to 200°C, and the reaction time is 0.1 to 24 hours.

[0024] According to a third aspect of this application, a positive electrode electrolyte is provided, the positive electrode electrolyte comprising a positive electrode electrolyte selected from the multi-electron transfer quinone derivatives described above;

[0025] The concentration of multi-electron transfer quinone derivatives in the positive electrode electrolyte is 0.02–5 mol / L.

[0026] Optionally, the concentration of the multi-electron-transfer quinone derivative in the positive electrode electrolyte is independently selected from any value among 0.02 mol / L, 0.05 mol / L, 0.1 mol / L, 0.5 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, and 5 mol / L, or a range between any two of the above.

[0027] Optionally, the concentration of the multi-electron-transfer quinone derivative in the positive electrode electrolyte is 0.5–2 mol / L.

[0028] According to a fourth aspect of this application, an aqueous organic flow battery is provided, the aqueous organic flow battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte;

[0029] The positive and negative electrodes are independently selected from at least one of carbon felt, carbon cloth, carbon paper, graphite plate, and metal plate;

[0030] The diaphragm separates the positive and negative electrodes, dividing them into a positive electrode side cavity and a negative electrode side cavity;

[0031] The positive electrode side cavity is provided with a positive electrode electrolyte, and the negative electrode side cavity is provided with a negative electrode electrolyte;

[0032] The positive electrode electrolyte is selected from the positive electrode electrolytes described above;

[0033] The negative electrode electrolyte in the negative electrode electrolyte solution is selected from at least one of vanadium dichloride, silicotungstic acid, stannous chloride, cadmium chloride, chromium chloride, lead sulfate, and titanium sulfate.

[0034] Optionally, the positive and negative electrolytes may further contain a supporting electrolyte.

[0035] Optionally, the supporting electrolyte is selected from at least one of hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid, acetic acid, methanesulfonic acid, and trifluoromethanesulfonic acid.

[0036] Optionally, the concentration of the supporting electrolyte is 0.1 to 4 mol / L.

[0037] Optionally, the concentration of the supporting electrolyte is independently selected from any value of 0.1 mol / L, 0.5 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, or a range between any two of the above.

[0038] Optionally, the concentration of the supporting electrolyte is 1 to 2 mol / L.

[0039] Optionally, in the aqueous organic flow battery, the negative electrode electrolyte is a solution with a total concentration of negative electrode electrolyte from 0.05 mol / L to its saturation concentration.

[0040] As an optional implementation, this application is achieved through the following technical solution:

[0041] An organic flow battery includes a single cell or a stack of two or more single cells; the single cell includes a positive electrode, a separator, and a negative electrode, wherein a positive electrolyte is introduced between the positive electrode and the separator, and a negative electrolyte is introduced between the negative electrode and the separator, and the positive electrolyte in the positive electrolyte is a pyrene tetraketone derivative modified with a sulfonic acid group.

[0042] Preferred structures include PTO-PTS, 1-Br-PTO-PTS, and 1,6-Br-PTO-PTS. Firstly, the presence of a hydrophilic -SO3H group is preferred, as it enhances the water solubility of the PTO core, allowing it to be used in aqueous electrolytes at concentrations of 1M and above. Secondly, the introduction of electron-withdrawing Br groups at the R1 or R1,R4 positions further enhances the PTO potential. Furthermore, compared to modifications at the R3 and R6 positions in traditional organic synthesis and electrochemical applications, modifications at the R1 or R1,R4 positions reduce molecular polarity, thereby improving its solvation structure and preventing the active molecule from precipitating or forming during operation in aqueous organic flow batteries, thus improving the battery's cycle stability.

[0043]

[0044] The electrolyte utilizes a pyrene tetraketone derivative modified with sulfonic acid groups. A carbonyl redox center is introduced at positions 4, 5, 9, and 10 of the pyrene precursor via a low-cost metal-catalyzed oxidation reaction, followed by hydrophilic sulfonation to create a reversible redox couple. After dissolving in aqueous solution, it can be directly used as an electrolyte in aqueous organic flow batteries without further treatment. By controlling the precursor of this redox couple, two to four steps of four-electron transfer can be achieved during the redox process, resulting in a fourfold increase in volumetric capacity compared to traditional single-electron transfer organic active redox couples. Furthermore, the extended conjugated structure of the pyrene tetraketone core increases the electron delocalization range and enhances the rigidity of the organic framework, thus giving the redox couple excellent redox kinetics and cycling stability. In addition, the introduction of hydrophilic and electron-withdrawing sulfonic acid groups increases the solubility of the core and the electrode potential, allowing for an operational concentration exceeding 1 M. The flow battery composed of this redox couple with a vanadium anode has an open-circuit voltage of ~1 V and a volumetric capacity exceeding 90 Ah / L. -1Simultaneously, it exhibits stable cycling in air for up to 60 days with no capacity decay, while also improving kinetics at 80 mA / cm². -2 The energy efficiency is ~80% at this current density. Flow batteries assembled using this redox couple with electrolyte exhibit advantages such as low cost, high energy density, ultra-long cycle life, and high battery efficiency, showing great promise for large-scale energy storage applications.

[0045] The beneficial effects that this application can produce include:

[0046] 1) This application introduces four carbonyl redox active centers at the 4, 5, 9, and 10 positions of pyrene through low-cost metal-catalyzed oxidation. Simultaneously, the introduction of hydrophilic groups allows for dissolution in aqueous solution, enabling four-electron transfer and enhancing the activity of the parent core. This, in turn, improves the energy density of the organic flow battery from the perspective of multi-electron transfer, reducing the organic matter concentration to less than four times at the same energy density, thus saving electrolyte costs. Furthermore, the introduction of sulfonic acid groups optimizes the solvation structure of the parent core, ensuring good solubility in aqueous solution and preventing capacity decay caused by precipitation during cycling.

[0047] 2) The organic molecules used in this application modify the polar sulfonic acid groups to increase the molecular dipole moment, thereby increasing their solubility in the electrolyte to ~1M, thus significantly improving the energy density of the organic flow battery.

[0048] 3) The organic molecule used in this application can reduce the electron cloud density of the parent nucleus by utilizing the electron-withdrawing effect of the sulfonic acid group, thereby increasing its electrode potential. When combined with the vanadium anode to form an organic flow battery, its open-circuit voltage is ~1V, thereby significantly improving the output voltage and energy density of the organic flow battery.

[0049] 4) The active molecule of the organic flow battery provided in this application utilizes the conjugation extension strategy of the pyrene tetrake core, which enables its semiquinone radical to exist stably in an air atmosphere, achieve stable cycling of 5000 times, and run for more than 60 days. It also maintains stable cycling even under high temperature conditions of 60°C.

[0050] 5) The organic flow battery active molecule used in this application utilizes the highly conjugated structure of pyrene tetraketone to increase the degree of electron delocalization, thereby accelerating the electron transfer rate during the electrochemical reaction process, with an electron transfer rate constant of 10. -2 cm s -1 The battery has excellent rate performance, at 80mA cm -2 At current densities, the energy efficiency is close to 70%.

[0051] 6) The organic flow battery active molecules provided in this application benefit from the conjugated structure of pyrene tetraketone, which increases the size of the organic active molecules, thereby slowing down molecular permeation and maintaining stable capacity. The molecular permeation coefficient is ~10. -9 mol L -1 h -1 There is almost no capacity decay during cycling, and the requirements for the membrane are reduced.

[0052] 7) Some of the sulfonic acid group-modified pyrene tetraketone derivatives used in this application are inexpensive and readily available, thus the prepared electrolyte has the advantage of low price. Furthermore, pyrene, the raw material, is a polycyclic aromatic hydrocarbon widely used in other fields and is a common chemical raw material. Attached Figure Description

[0053] Figure 1 For the PTO in Embodiment 1 of this application 1 H NMR spectrum;

[0054] Figure 2 For the PTO-PTS in Embodiment 1 of this application 1 H NMR spectrum;

[0055] Figure 3 MS diagrams of different states of PTO-PTS in Embodiment 1 of this application;

[0056] Figure 4 For 1-Br-PTO in Embodiment 2 of this application 1 H NMR spectrum;

[0057] Figure 5 For 1-Br-PTO-PTS in Embodiment 2 of this application 1 H NMR spectrum;

[0058] Figure 6 MS images of different states of 1-Br-PTO-PTS in Embodiment 2 of this application;

[0059] Figure 7 For example, 1,6-Br-PTO in Embodiment 3 of this application 1 H NMR spectrum;

[0060] Figure 8 For example, 1,6-Br-PTO-PTS in Embodiment 3 of this application 1 H NMR spectrum;

[0061] Figure 9 MS images of different states of 1,6-Br-PTO-PTS in Embodiment 3 of this application;

[0062] Figure 10The cyclic voltammetry curve of PTO-PTS in 3M H2SO4 aqueous solution in Example 4 of this application;

[0063] Figure 11 The cyclic voltammetry curve of 1-Br-PTO-PTS in 3M H2SO4 aqueous solution in Example 4 of this application;

[0064] Figure 12 The cyclic voltammetry curve of 1,6-Br-PTO-PTS in 3M H2SO4 aqueous solution in Example 4 of this application;

[0065] Figure 13 The cyclic voltammogram of PTO-PTS in 3M H2SO4 solution in Example 5 of this application has a scan rate of 10mV / s to 200mV / s and an interval of 10mV / s.

[0066] Figure 14 This is a fitting graph of the peak current and the square root of the scan rate of the cyclic voltammetry of PTO-PTS in 3M H2SO4 solution in Example 5 of this application.

[0067] Figure 15 The cyclic voltammogram of 1-Br-PTO-PTS in 3M H2SO4 solution in Example 5 of this application is shown. The scan rate is 10mV / s to 200mV / s and the interval is 10mV / s.

[0068] Figure 16 This is a fitting graph of the peak current versus the square root of the scan rate for the cyclic voltammetry of 1-Br-PTO-PTS in 3M H2SO4 solution in Example 5 of this application.

[0069] Figure 17 The cyclic voltammogram of 1,6-Br-PTO-PTS in 3M H2SO4 solution in Example 5 of this application is shown. The scan rate is 10mV / s to 200mV / s and the interval is 10mV / s.

[0070] Figure 18 This is a fitting graph of the peak current versus the square root of the scan rate for the cyclic voltammetry of 1,6-Br-PTO-PTS in 3M H2SO4 solution in Example 5 of this application.

[0071] Figure 19-26 The test results of the rotating disk electrode of PTO-PTS in this application;

[0072] Figure 27-36 The test results of the rotating disk electrode of 1-Br-PTO-PTS in this application;

[0073] Figure 37-42 The test results of the rotating disk electrode of 1,6-PTO-PTS in this application;

[0074] Figure 43 The battery assembled with PTO-PTS in Example 7 of this application operates at 40 mA / cm. 2 Cyclic performance at current density;

[0075] Figure 44 This is a charge-discharge curve of the battery assembled by PTO-PTS in Embodiment 7 of this application for different cycles;

[0076] Figure 45 The battery assembled with 1-Br-PTO-PTS in Example 8 of this application operates at 10 mA / cm. 2 Cyclic performance at current density;

[0077] Figure 46 This is a charge-discharge curve of the battery assembled with 1-Br-PTO-PTS in Example 8 of this application for different cycles.

[0078] Figure 47 The battery assembled with 1,6-PTO-PTS in Example 9 of this application operates at 10 mA / cm². 2 Cyclic performance at current density;

[0079] Figure 48 This is a charge-discharge curve of the battery assembled with 1,6-PTO-PTS in Example 9 of this application for different cycles.

[0080] Figure 49 This is a rate performance diagram of the PTO-PTS assembled battery in Example 10 of this application under different current density charge and discharge conditions;

[0081] Figure 50 This application presents a comparison of the energy efficiency of batteries assembled with PTO-PTS, 1-Br-PTO-PTS, and 1,6-PTO-PTS in Example 10 of this application under different current density charge and discharge conditions.

[0082] Figure 51 The battery assembled with 1.0M PTO-PTS in Example 11 of this application operates at 20mA / cm. 2 Cyclic performance at current density;

[0083] Figure 52 The impedance spectra before and after the PTO-PTS cycle in Example 12 of this application are shown.

[0084] Figure 53 This is a linear fit graph of the permeation concentration versus time obtained by the permeation test of PTO-PTS in Example 13 of this application;

[0085] Figure 54The cycle stability test of PTO as the positive electrode material in lithium-ion battery was carried out in Comparative Example 1 of this application.

[0086] Figure 55 The cycling stability test of 1-Br-PTO as the positive electrode material in Comparative Example 2 of this application was carried out in a lithium-ion battery.

[0087] Figure 56 The cycling stability test of 1,6-Br-PTO as the cathode material in Comparative Example 3 of this application was carried out in a lithium-ion battery.

[0088] Figure 57 The battery assembled with the 1.0M PTO-PTS in application 11 operates at 10mA / cm 2 Charge-discharge curves at current density. Detailed Implementation

[0089] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0090] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0091] Example 1

[0092] Chemical synthesis of sulfonic acid group-modified pyrene tetradone derivative precursors:

[0093] 10 g of pyrene (98%) was slowly dissolved in 100 mL of a mixed solution of dichloromethane, acetonitrile, and water (volume ratio 1:1:1.25). 1.25 equivalents of 20 mg of ruthenium trichloride hydrate and 5.0 equivalents of sodium periodate solid were added. After the pyrene was completely dissolved, the solution was stirred at room temperature for 12 hours. The solution was then purified by column chromatography using dichloromethane as the eluent. The solution was rotary evaporated and dried in a vacuum oven at 60 °C to obtain the pyrene tetraketone precursor, abbreviated as PTO. 10 mg of PTO powder was then dissolved in 1 mL of deuterated chloroform. 1 H NMR image as follows Figure 1 As shown, through 1 ¹H NMR indicates that PTO has high purity and no other impurities are detected.

[0094] Subsequently, 10 mg of PTO powder precursor was taken, 1.25 equivalents of fuming sulfuric acid were added, and the mixture was stirred and heated at 180°C for 1 hour. After adding 0.1 g of sodium chloride crystals, the mixture was cooled and crystallized. The solid was collected to obtain the sulfonated pyrene-tetraone derivative, abbreviated as PTO-PTS.

[0095] Weigh 10 mg of PTO-PTS powder and dissolve it in 1 mL of deuterated chloroform and sulfuric acid aqueous solution, respectively. 1 The H NMR and MS mass spectra are as follows: Figure 2 As shown in Figure 3, through1 The H NMR and MS mass spectra show that PTO-PTS has high purity and no signals from other impurities.

[0096]

[0097] Example 2

[0098] 10 g of 1-bromo-pyrene (98%) was slowly dissolved in 50 mL of a mixed solution of acetonitrile and water (volume ratio 1:1.25). 1.25 equivalents of 20 mg of ruthenium trichloride hydrate and 5.0 equivalents of sodium periodate solid were added. After complete dissolution of 1-bromo-pyrene, the solution was stirred at 50 °C for 12 hours. The solution was then washed with methanol, filtered to obtain a filter cake, and dried in a vacuum oven at 60 °C to obtain the 1-bromo-pyrene tetraketone precursor, abbreviated as 1-Br-PTO. 10 mg of 1-Br-PTO powder was weighed and dissolved in 1 mL of deuterated chloroform. 1 H NMR image as follows Figure 4 As shown, through 1 ¹H NMR showed that 1-Br-PTO was of high purity and contained no other impurities.

[0099] Subsequently, 10 mg of 1-Br-PTO powder precursor was taken, and 1.25 equivalents of fuming sulfuric acid were added. After stirring, the mixture was heated at 80°C for 12 h. Then, 0.1 g of sodium chloride crystals were added, and the mixture was cooled to crystallize. The solid was collected to obtain the sulfonated 1-bromopyrene tetratone derivative, abbreviated as PTO-PTS.

[0100] 10 mg of 1-Br-PTO-PTS powder was dissolved in 1 mL of deuterated chloroform and sulfuric acid aqueous solution, respectively. The 1H NMR and MS mass spectra are shown below. Figure 5 As shown in Figure 6, the 1H NMR and MS mass spectra show that 1-Br-PTO-PTS has high purity and no other impurity signals.

[0101]

[0102] Example 3

[0103] 10 g of 1,6-bromo-pyrene (98%) was slowly dissolved in 50 mL of a mixed solution of acetonitrile and water (volume ratio 1:1.25). 1.25 equivalents of 20 mg of ruthenium trichloride hydrate and 5.0 equivalents of sodium periodate solid were added. After the 1-bromo-pyrene was completely dissolved, the solution was stirred at 50 °C for 12 hours. The solution was then washed with methanol, filtered to obtain a filter cake, and dried in a vacuum oven at 60 °C to obtain the 1,6-bromo-pyrene tetraketone precursor, abbreviated as 1,6-Br-PTO. 10 mg of 1,6-Br-PTO powder was weighed and dissolved in 1 mL of deuterated chloroform. 1 H NMR image as follows Figure 7 As shown, through 1¹H NMR showed that 1,6-Br-PTO was of high purity and contained no other impurities.

[0104] Subsequently, 10 mg of 1,6-Br-PTO powder precursor was taken, and 1.25 equivalents of fuming sulfuric acid were added. After stirring, the mixture was heated at 200°C for 2 hours. Then, 0.1 g of sodium chloride crystals were added, and the mixture was cooled to crystallize. The solid was collected to obtain the sulfonated 1,6-bromopyrene tetratone derivative, abbreviated as 1,6-Br-PTO-PTS.

[0105] Weigh 10 mg of 1,6-Br-PTO-PTS powder and dissolve it in 1 mL of deuterated chloroform and sulfuric acid aqueous solution, respectively. 1 The H NMR and MS mass spectra are as follows: Figure 8 As shown in Figure 9, through 1 The H NMR and MS mass spectra show that PTO-PTS has high purity and no signals from other impurities.

[0106]

[0107] Charge-discharge test of PTO-PTS active couple:

[0108] A certain amount of PTO-PTS, 1-Br-PTO-PTS, and 1,6-Br-PTO-PTS powders were dissolved in sulfuric acid aqueous solution as the electrolyte and used as the positive electrode. The mixture was then combined with silicotungstic acid or vanadium negative electrode for discharge testing. During the process, the active molecules in the positive electrode electrolyte could undergo carbonyl reduction of hydroxyl groups. Upon recharging, the hydroxyl groups would be reversibly oxidized to carbonyl groups, resulting in a redox couple that could achieve four-electron four-proton coupling.

[0109] Example 4

[0110] PTO-PTS, 1-Br-PTO-PTS, and 1,6-Br-PTO-PTS solids were dissolved in 10 ml of 3M H₂SO₄ of different concentrations, and the solutions were shaken and stirred until a homogeneous solution was formed, resulting in a 5 mmol / L solution. Cyclic voltammetry was performed on the prepared electrolyte using a three-electrode system, with silver / silver chloride as the reference electrode and graphite electrodes as the working and counter electrodes. The scan rate was 50 mV / s. Figure 10-12Cyclic voltammetry confirmed that the electron-withdrawing effect of the sulfonic acid group slightly increases the HOMO orbital of the pyrene tetraketone core, resulting in electrode potentials of PTO-PTS of ~0.30, 0.46, and 0.60 V vs. SHE. For 1-Br-PTO-PTS, the electrode potentials were ~0.29 and 0.64 V vs. SHE, while for 1,6-Br-PTO-PTS, the potentials were ~0.034, 0.32, 0.42, and 0.59 V vs. SHE. This demonstrates that by controlling the electron cloud density of the precursor, the intermediate product can be stabilized, and the Gibbs free energy of the reaction can be controlled to achieve two-step, three-step, and four-step four-electron transfers, thereby optimizing the battery's energy efficiency.

[0111] Example 5

[0112] PTO-PTS, 1-Br-PTO-PTS, and 1,6-Br-PTO-PTS solids were dissolved in 3M H₂SO₄ solution as the electrolyte. The electrolyte was diluted to 5mM for cyclic voltammetry testing. The prepared electrolyte was used in a three-electrode system for cyclic voltammetry testing, with silver / silver chloride as the reference electrode and graphite electrodes as the working and counter electrodes. The scan rate was 10mV / s to 100mV / s, and the interval was 10mV / s. Figure 13 As shown in 15 and 17, there is no significant peak shift as the scanning speed increases; and from Figure 14 As shown in 16 and 18, the peak current and the square root of the scanning speed follow a linear relationship, indicating that the redox couple of the hydrophilized pyrene tetraketo derivative is reversible.

[0113] Example 6

[0114] PTO-PTS, 1-Br-PTO-PTS, and 1,6-Br-PTO-PTS solids were dissolved in 3M H₂SO₄ solution as the electrolyte. The solution was diluted to 0.5 mM for linear sweep voltammetry (LSV) using a three-electrode system. A rotating disk electrode (RDE, Shanghai Chuxi Co., Ltd.) was used as the working electrode, with an effective electrode area of ​​0.1963 cm⁻². 2 The reference electrode is a mercury oxide electrode (Shanghai Chuxi Co., Ltd.). The counter electrode is a graphite electrode with an effective area of ​​9 cm². 2 (3cm×3cm, Jiangsu Shenzhou Carbon Products Co., Ltd.). The testing instrument was a BioLogic VMP3 electrochemical workstation. The testing conditions were a scan rate of 5 mV / s. -1 The voltage range was 0.8 to -0.2V vs. Ag / AgCl. During the test, the working electrode RDE rotation speed was 500–4000 rpm, with a test performed every 500 rpm increase. The test results are as follows: Figure 19-42 As shown.

[0115] The measured limiting diffusion current i and the square root of the rotational speed ω 1 / 2 The fitting was performed, and the fitting result is as follows: Figure 20 As shown in 28 and 38, Figure 20 Figures 28 and 38 schematically illustrate the limiting current i as a function of the square root ω of the rotational speed. 1 / 2 The relationship between the changes, i.e., the Levich curve, is used to calculate the diffusion coefficient D using the Levich equation: i = 0.620nFAcD 2 / 3 υ -1 / 6 ω 1 / 2

[0116] Where i is the limiting diffusion current; n is the charge transfer number, n = 1; F represents the Faraday constant, which is 96485 C mol. -1 A represents the area of ​​the electrode, which is 0.196 cm². -2 c represents the electrolyte concentration, which is 0.05 mM / L. -1 υ is 3 mol L -1 H2SO4 supports the kinetic viscosity of the electrolyte; D represents the diffusion coefficient of electrolyte molecules; ω is the set rotational speed of the electrode.

[0117] At different overpotentials, the reciprocal of the current 1 / i divided by the reciprocal of the square root of the rotational speed ω -1 / 2 Perform linear fitting, and the fitting result is as follows: Figure 21-23 As shown in 29-32, 38-39, Figure 21-23 Peaks 29-32 and 39-40 represent the three pairs of redox peaks of PTO-PTS, the four pairs of redox peaks of 1-Br-PTO-PTS, and the two pairs of redox peaks of 1,6-Br-PTO-PTS under different overpotentials. The reciprocal of the current 1 / i and the reciprocal of the square root of the rotational speed ω are also relevant. -1 / 2 The relationship between the two (Koutecky-Levich analysis) is used to obtain the dynamic control current i. k Then, the overpotential (η) and dynamic current (i) are analyzed. k A linear fit was performed, and the fitting result is as follows: Figure 24-26 Figures 33-36 and 41-42 show the Butler-Volmer equation fitting curves schematically. The exchange current i0 is obtained from the intercept of the fitted line, and the electron transfer rate constant k0 is obtained based on the Butler-Volmer equation: i0 = nFAck0. The results show that the diffusion coefficients of the three redox peaks of PTO-PTS are ~10. -6 cm 2 s -1 The charge transfer rate constant is 10. -2 m S -1The diffusion coefficients of the four redox peaks of 1-Br-PTO-PTS and the two redox peaks of 1,6-Br-PTO-PTS are ~10. -7 cm 2 s -1 The charge transfer rate constant is 10. -3 m S -1 .

[0118] In summary, by Figure 24-26 It is evident that the diffusion coefficients and electron transfer constants of the three redox peaks in PTO-PTS are extremely high, placing them at an advanced level among active redox couples used in current flow batteries. This indicates that the reversible redox couple undergoing this four-electron transfer exhibits extremely fast electrode reaction kinetics, thereby contributing to improved rate performance of organic flow batteries. Furthermore, through comparison... Figure 27-42 It can be seen that the diffusion coefficients and electron transfer constants of the four redox peaks of 1-Br-PTO-PTS and the two redox peaks of 1,6-Br-PTO-PTS are slightly lower than those of PTO-PTS. This indicates that the introduction of Br atoms increases the Stokes radius of the active molecule, which is not conducive to the diffusion and charge transfer of the active molecule.

[0119] Example 7

[0120] Application of pyrene tetraketone derivatives based on four-electron transfer in aqueous organic flow batteries

[0121] The PTO-PTS prepared in Example 1 was weighed and dissolved in a 3 mol / L sulfuric acid solution. The solution was shaken and stirred until a homogeneous solution was formed, resulting in a 0.12 mol / L solution, which was then used as the positive electrode electrolyte. A commercially available vanadium electrolyte was pre-electrolyzed, and the negative electrode V(II) was used as the negative electrode electrolyte. The above electrolyte was connected to a flow battery device as both the positive and negative electrode electrolytes. The battery was assembled according to the sequence and position of the graphite current collector, carbon felt electrode, ion exchange membrane, graphite felt electrode, and graphite current collector. The battery was charged and discharged in an air atmosphere using a peristaltic pump to drive the liquid.

[0122] like Figures 43-44 As shown, this flow battery operates at 40 mA / cm². 2 Under a current density of ~11 Ah / L, the battery is subjected to long charge-discharge cycles. The discharge capacity is ~11 Ah / L, the four-electron utilization rate is ~90%, and after 5000 cycles (60 days), the capacity retention rate is ~100%, the coulombic efficiency is close to 100%, and the energy efficiency is about 80%.

[0123] Example 8

[0124] The 1-Br-PTO-PTS prepared in Example 2 was weighed and dissolved in a 3 mol / L sulfuric acid solution. The solution was shaken and stirred until a homogeneous solution was formed, resulting in a 0.01 mol / L solution, which was then used as the positive electrode electrolyte. A commercial vanadium electrolyte was pre-electrolyzed, and the negative electrode V(II) was used as the negative electrode electrolyte. The above electrolyte was connected to a flow battery device as both the positive and negative electrode electrolytes. The battery was assembled according to the sequence and position of the graphite current collector, carbon felt electrode, ion exchange membrane, graphite felt electrode, and graphite current collector. The battery was charged and discharged in an air atmosphere using a peristaltic pump to drive the liquid.

[0125] like Figures 45-46 As shown, this flow battery operates at 10 mA / cm². 2 Under a current density of ~0.6 Ah / L, the discharge capacity is ~88% and the four-electron utilization rate is ~88%. After 2000 cycles (~23 days), the capacity retention rate is ~100%, the coulombic efficiency is close to 100%, and the energy efficiency is about 50%.

[0126] Example 9

[0127] The 1,6-Br-PTO-PTS prepared in Example 3 was weighed and dissolved in a 3 mol / L sulfuric acid solution. The solution was shaken and stirred until a homogeneous solution was formed, resulting in a 0.02 mol / L solution, which was then used as the positive electrode electrolyte. A commercial vanadium electrolyte was pre-electrolyzed, and the negative electrode V(II) was used as the negative electrode electrolyte. The above electrolyte was connected to a flow battery device as both the positive and negative electrode electrolytes. The battery was assembled according to the sequence and position of graphite current collector, carbon felt electrode, ion exchange membrane, graphite felt electrode, and graphite current collector. The battery was charged and discharged in an air atmosphere using a peristaltic pump to drive the liquid.

[0128] like Figures 47-48 As shown, this flow battery operates at 10 mA / cm². 2 Under a current density of ~1.2 Ah / L, the discharge capacity is ~90% and the four-electron utilization rate is ~90%. After 800 cycles (~21 days), the capacity retention rate is ~100%, the coulombic efficiency is close to 100%, and the energy efficiency is about 70%.

[0129] Example 10

[0130] like Figure 49 As shown, at 10, 20, 40, 60, and 80 mA / cm 2 The battery in Example 8 was charged and discharged at a current density of ~100%. Due to the influence of film resistance, the voltage efficiency and energy efficiency decreased with increasing current density, but remained stable at 80 mA / cm². 2 At high current densities, energy efficiency can reach 70%. And as... Figure 50It is evident that PTO-PTS exhibits significantly higher energy efficiency than 1-Br-PTO-PTS and 1,6-Br-PTO-PTS. This is primarily due to the superior diffusion coefficient and electron transfer constant of PTO-PTS, resulting in better diffusion and charge transfer processes compared to the latter. Furthermore, compared to 1,6-Br-PTO-PTS, its redox peak spacing is smaller, which helps to avoid voltage drops during charge and discharge processes, thus improving both voltage and energy efficiency. Additionally, compared to 1-Br-PTO-PTS, its superior diffusion coefficient and reduced charge transfer steps contribute to achieving even better energy efficiency.

[0131] Example 11

[0132] The PTO-PTS prepared in Example 1 was weighed and dissolved in a 1 mol / L sulfuric acid solution. The solution was shaken and stirred until a homogeneous solution was formed, resulting in a 1.0 mol / L solution, which was then used as the positive electrode electrolyte. This solution was placed in a constant temperature chamber at approximately 60°C. A commercially available vanadium electrolyte was pre-electrolyzed, and the negative electrode V(II) was used as the negative electrode electrolyte. The above electrolyte was connected to a flow battery device as both the positive and negative electrode electrolytes. The battery was assembled according to the sequence and position of the graphite current collector, carbon felt electrode, ion exchange membrane, graphite felt electrode, and graphite current collector. The battery was charged and discharged using a peristaltic pump driven by air.

[0133] like Figure 51 As shown, this flow battery operates at 20 mA / cm². 2 Under high current density, long charge-discharge cycles were performed, with a discharge capacity of ~90 Ah / L, and almost no capacity decay after 300 cycles. Meanwhile, as... Figure 57 It can be seen that it is at 10mA / cm 2 The discharge capacity exceeds 90 Ah L -1 It exhibits low polarization between charge and discharge plateaus and good reversibility.

[0134] Example 12

[0135] The assembled batteries underwent impedance testing during the initial cycling phase, with scanning in the range of 1 kHz to 1 MHz, and EIS curves were recorded. Furthermore, after 60 days of cycling, the batteries were subjected to impedance testing under the same conditions to investigate impedance changes before and after long-term cycling. Figure 52 It can be seen that the battery impedance remains almost unchanged before and after long cycling, both being less than 1Ω, indicating that the molecular stability is good throughout the cycling process, which is conducive to obtaining a long cycle life.

[0136] Example 13

[0137] The permeability of the pyrene tetraketone derivative electrolyte modified with sulfonic acid groups at the positive electrode was tested using a permeation cell (made of plexiglass). The test membrane material (PBI dense membrane) was placed in the middle of the permeation cell. The solution on the left side of the permeation cell was 80 mL of 0.15 MPa TO-PTS + 3 M H2SO4 solution. The solution on the right side of the permeation cell was 80 mL of 3 M H2SO4 solution. Magnetic stirring was used on both sides of the permeation cell throughout the test to reduce concentration polarization. During the test, 3 mL of the test solution was taken from the solution on the right side of the permeation cell at fixed intervals, and the same volume of 3 M H2SO4 solution was added simultaneously to maintain a constant volume. The concentration of the target substance in the test solution was measured using a UV-Vis spectrophotometer (Beijing Purkinje General, TU-1901).

[0138] Depend on Figure 53 As is known, the molecular permeability coefficient is ~10. -9 mol L -1 h -1 This indicates that the large conjugated structure of pyrene tetraketone increases the size of organic active molecules, thereby slowing down molecular permeation, maintaining stable capacity, with almost no capacity decay during cycling, and reducing the requirements on the membrane.

[0139] Comparative Example 1

[0140] The PTO obtained in Example 1 was used as the positive electrode material in a lithium-ion battery for cycle stability testing. The battery composition was as follows: the prepared PTO positive electrode material was dissolved in NMP in a ratio of active material: conductive agent: binder = 7:2:1 to form a slurry, which was then used as the positive electrode of the lithium-ion battery. A lithium metal sheet was used as the negative electrode, a glass fiber membrane was used as the separator, the solute was 1MLiClO4 (lithium perchlorate), the solvent was a mixture of EC (ethylene carbonate) and DEC (diethyl carbonate) (mass ratio 1:1), the additive was 2% FEC as the electrolyte, and aluminum foil was used as the current collector. The negative electrode shell, negative electrode, electrolyte, separator, electrolyte, positive electrode, current collector, and positive electrode shell were stacked and pressed together in sequence to form a CR2016 coin cell lithium-ion battery.

[0141] The test conditions were: room temperature 25℃, dry constant temperature chamber; the test results are as follows: Figure 54 As shown. By Figure 54 It can be seen that the specific capacity of Comparative Example 1 can reach 250mAh g. -1 The specific capacity is lower than that of Example 7 (320 mAh g). -1 Furthermore, its rate performance is poor, exhibiting only 25mAh g at a 5C rate. -1The lower specific capacity is mainly due to the low conductivity of the PTO core, which leads to kinetic stagnation during the solid-phase reaction. Furthermore, its cycling stability is significantly lower than that of Example 7. Comparative Example 1, after 200 cycles at 1C, exhibits a capacity retention of less than 60%, primarily due to the reduction in active component content caused by the dissolution of organic molecules in the electrolyte, indicating significantly lower cycling stability compared to the examples.

[0142] Comparative Example 2

[0143] The 1-Br-PTO obtained in Example 2 was used as the positive electrode material in a lithium-ion battery for cycle stability testing. The battery composition was as follows: the prepared 1-Br-PTO positive electrode material was dissolved in NMP in a ratio of active material: conductive agent: binder = 7:2:1 to form a slurry, which was then used as the positive electrode of the lithium-ion battery. A lithium metal sheet was used as the negative electrode, a glass fiber membrane was used as the separator, the solute was 1M LiClO4 (lithium perchlorate), the solvent was a mixture of EC (ethylene carbonate) and DEC (diethyl carbonate) (mass ratio 1:1), the additive was 2% FEC as the electrolyte, and aluminum foil was used as the current collector. The negative electrode shell, negative electrode, electrolyte, separator, electrolyte, positive electrode, current collector, and positive electrode shell were stacked and pressed together in sequence to form a CR2016 coin cell lithium-ion battery.

[0144] The test conditions were: room temperature 25℃, dry constant temperature chamber; the test results are as follows: Figure 55 As shown. By Figure 55 It can be seen that the specific capacity of Comparative Example 2 can reach 204 mAh g. -1 The specific capacity is lower than that of Example 8 (256 mAh g). -1 Furthermore, its rate performance is poor, exhibiting only 10.2 mAh g at 5C. -1 The low specific capacity is mainly due to the low conductivity and poor rate performance of the 1-Br-PTO molecule. Furthermore, the introduction of bromine atoms reduces the proportion of active material, thus lowering the theoretical specific capacity of the electrode material. Simultaneously, its cycle stability is significantly lower than that of Example 8. Comparative Example 2, after 200 cycles at 1C, exhibited a capacity retention of less than 65%, primarily due to the reduction in active component content caused by the dissolution of organic molecules in the electrolyte. While the introduction of bromine atoms can alleviate the capacity decay caused by the dissolution of the PTO core in the electrolyte to some extent, the effect is not significant, and its cycle stability is significantly lower than that of the Example 8.

[0145] Comparative Example 3

[0146] The 1,6-Br-PTO obtained in Example 3 was used as the positive electrode material in a lithium-ion battery for cycle stability testing. The battery composition was as follows: the prepared 1,6-Br-PTO positive electrode material was dissolved in NMP in a ratio of active material: conductive agent: binder = 7:2:1 to form a slurry, which was then used as the positive electrode of the lithium-ion battery. A lithium metal sheet was used as the negative electrode, a glass fiber membrane was used as the separator, the solute was 1M LiClO4 (lithium perchlorate), the solvent was a mixture of EC (ethylene carbonate) and DEC (diethyl carbonate) (mass ratio 1:1), the additive was 2% FEC as the electrolyte, and aluminum foil was used as the current collector. The negative electrode shell, negative electrode, electrolyte, separator, electrolyte, positive electrode, current collector, and positive electrode shell were stacked and pressed together in sequence to form a CR2016 coin cell lithium-ion battery.

[0147] The test conditions were: room temperature 25℃, dry constant temperature chamber; the test results are as follows: Figure 56 As shown. Test conditions were: room temperature 25℃, dry constant temperature chamber; test results are as follows. Figure 56 As shown. By Figure 56 It can be seen that the specific capacity of Comparative Example 3 can reach 102 mAh g. -1 Slightly lower than the specific capacity of Example 9 (116 mAh g). -1 Furthermore, its rate performance is poor, exhibiting only 22.7 mAh g at 5C. -1 The low specific capacity is mainly due to the low conductivity of 1,6-Br-PTO, which leads to kinetic stagnation during the solid-phase reaction. Furthermore, the introduction of bromine atoms increases the proportion of inactive materials, reducing the theoretical specific capacity of the electrode material. Simultaneously, its cycle stability is significantly lower than that of Example 9. Comparative Example 3, after 200 cycles at 1C, exhibits a capacity retention of less than 72%, primarily due to the reduction in active component content caused by the dissolution of organic molecules in the electrolyte. While the introduction of bromine atoms can alleviate the capacity decay caused by the dissolution of the PTO core in the electrolyte to some extent, its cycle stability is still significantly lower than that of the examples. Additionally, it results in a significant problem of low utilization of active materials. This example demonstrates that modifying an aqueous organic flow battery with hydrophilic groups can avoid the low capacity utilization problem caused by the introduction of inactive groups and significantly improve the battery's cycle stability.

[0148] The above results indicate that the sulfonic acid group-modified pyrene tetradone derivatives have an actual operating concentration exceeding 1 M and a volumetric capacity exceeding 90 Ah / L. -1 This is beneficial for achieving higher battery energy density. In addition, thanks to the ultra-large conjugated structure of the pyrene tetraketone core, the stability of pyrenequinone derivatives modified with sulfonic acid groups is greatly improved, which is conducive to promoting the practical application of organic flow batteries.

[0149] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A multi-electron transfer quinone derivative, characterized in that, The multi-electron transfer quinone derivative has a structure shown in formula I: In formula I, R1, R2, R3, R4, R5, R6are independently selected from -H, -OH, -F, -Cl, -Br, -CN, -NH2, -N(CH3)2, -N(CH3)3 + , -OH, -SH, -OCH3, -SiH3, -CHO, -CF3, -COOH, -COOCH3, -CONH2, -NO2, -PO3H2, -SO3H, C1-C5 alkyl.

2. The multi-electron transfer quinone derivative according to claim 1, wherein At least one of R1, R2, R3, R4, R5 and R6 is -SO3H.

3. Process for the preparation of a multi-electron transfer quinone derivative according to any one of claims 1 to 2, characterized in that, The preparation method comprises the following steps: (1) mixing pyrene compound, catalyst, oxidant and solvent to obtain mixture I, and reacting I to obtain pyrene tetrone precursor; (2) mixing pyrene tetrone precursor and fuming sulfuric acid to obtain mixture II, and reacting II to obtain the multi-electron transfer quinone derivative.

4. The production method according to claim 3, characterized by, The pyrene compound is at least one selected from pyrene, 1-bromo-pyrene, 1,6-bromo-pyrene, 1-hydroxypyrene, 1-carboxypyrene, 1-methanol pyrene, 1-formic acid pyrene, 1-butanoic acid pyrene and 1-pyrene-BETA-D-glucuronate; Preferably, the catalyst is at least one selected from ruthenium trichloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, tris(dibenzylideneacetone)dipalladium(0) and palladium acetate; Preferably, the oxidant is at least one selected from sodium periodate, potassium permanganate, potassium dichromate, cerium trioxide, periodic acid, potassium periodate and calcium periodate; Preferably, the solvent is at least one selected from dichloromethane, acetonitrile, water, toluene, dimethyl sulfoxide, dimethylformamide, ethanol and methanol.

5. The preparation method according to claim 3, characterized in that, In step (1), the molar ratio of the pyrene compound to the catalyst is 100-1000:1; Preferably, the molar ratio of the pyrene compound to the oxidant is 4-6:1; Preferably, the amount of the pyrene compound used in the solvent is 40-400 g / L.

6. The preparation method according to claim 3, characterized in that, In step (1), the temperature of reaction I is 0-100℃, and the reaction time of reaction I is 2-24 h; Preferably, in step (2), the molar ratio of the pyrene tetrone precursor to the fuming sulfuric acid is 1-4:1; Preferably, in step (2), the temperature of reaction II is 0-200℃, and the reaction time of reaction II is 0.1-24 h.

7. A positive electrolyte, characterized by comprising: The positive electrolyte comprises a positive electrolyte selected from the multi-electron transfer quinone derivative according to any one of claims 1-2; In the positive electrolyte, the concentration of the multi-electron transfer quinone derivative is 0.02-5 mol / L.

8. The positive electrolyte according to claim 7, characterized in that, In the positive electrolyte, the concentration of the multi-electron transfer quinone derivative is 0.5-2 mol / L.

9. An aqueous organic flow battery, characterized in that, The aqueous organic flow battery comprises a positive electrode, a negative electrode, a separator and an electrolyte; The positive electrode and the negative electrode are independently at least one selected from carbon felt, carbon cloth, carbon paper, graphite plate and metal plate; The separator separates the positive electrode and the negative electrode into a positive electrode side cavity and a negative electrode side cavity; The positive electrode side cavity is provided with a positive electrolyte, and the negative electrode side cavity is provided with a negative electrolyte; The positive electrolyte is selected from the positive electrolyte according to any one of claims 7-8; The negative electrolyte comprises a negative electrolyte selected from at least one of vanadium dichloride, silicotungstic acid, stannous chloride, cadmium chloride, chromous chloride, lead sulfate and titanium sulfate.

10. The aqueous organic flow battery of claim 9, wherein, The positive electrolyte and the negative electrolyte further comprise a supporting electrolyte; Preferably, the supporting electrolyte is at least one selected from hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid, acetic acid, methyl sulfonic acid and trifluoromethanesulfonic acid. Preferably, the concentration of the supporting electrolyte is 0.1-4 mol / L. Preferably, the concentration of the supporting electrolyte is 1-2 mol / L.

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