Sulfur-containing group via vien derivatives, methods of making and use in flow battery systems

Abstract

The application discloses a chalcogen-containing viologen derivative, a preparation method thereof and application of the chalcogen-containing viologen derivative in a flow battery system. The elements contained in the molecule include carbon, hydrogen, nitrogen, oxygen and chalcogen, and the molecule is rich in resources, low in cost and simple in synthesis method. Compared with a traditional bipyridine compound, the introduction of the chalcogen in the middle of the pyridine unit enhances the conjugation of the whole molecule structure and improves the stability of the molecule. The hydrophilic group is introduced into the nitrogen atom through ionization, the water solubility is increased, and the molecule can be used in a more green and environmental neutral aqueous flow battery. Tests show that the neutral aqueous flow battery composed of the molecule as an anode and ferrocene as a cathode has excellent performance, is stable in circulation and has a long service life, and has a good application prospect in the field of large-scale energy storage.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of energy storage material preparation, and particularly relates to a kind of sulfur group element-containing viologen derivative, a preparation method thereof and application thereof in a flow battery system. BACKGROUND

[0002] Nowadays, environmental problems are becoming more and more serious, and traditional energy is becoming increasingly scarce. New renewable clean energy such as solar power generation, wind power generation, and tidal power generation accounts for an increasing proportion in power supply. However, there are problems such as randomness, volatility, and intermittency in power generation relying solely on natural energy such as solar energy and wind energy. Unstable power output will affect the smooth operation of the power grid system to some extent, which greatly limits the development of new energy power supply technology. In order to solve this problem, energy storage technology will be the key. Stable and efficient energy storage technology can effectively store new energy power generation, and further meet the urgent needs of peak load shifting, smooth output, and frequency and amplitude modulation. Therefore, it is necessary to research and apply large-scale energy storage technology. Among various energy storage technologies, electrochemical energy storage can highly meet the requirements of different scale power grids due to its advantages such as pollution-free operation, high energy efficiency, low maintenance cost, and no time and space limitations.

[0003] Among various electrochemical energy storage technologies, flow batteries have a unique structure in which the electrolyte storage tanks of the anode and the cathode are separated from the power stack, which allows independent and flexible design of the charge and discharge power and the battery capacity. The flexible scalability and excellent modularity of the flow battery are very suitable for the needs of new energy power stations for energy storage technology. In recent years, the mature all-vanadium flow battery has played an important role. However, the all-vanadium flow battery also has some disadvantages that are difficult to solve, such as the high price and toxicity of vanadium, the limitation of single electron transfer process on energy density, the poor stability of the battery due to the penetration of vanadium ions through the separator in actual use, and the corrosion of the battery components by the acidic electrolyte. In contrast, the electrolyte materials of the neutral aqueous organic flow battery mainly contain non-metallic elements such as C, H, O, and N, which are low in cost and non-toxic and non-polluting. The use of neutral sodium chloride or potassium chloride aqueous solution greatly reduces the corrosion of the electrolyte on the battery system, reduces the cost, and makes the system more safe and stable, which is a very promising new generation of flow battery system.

[0004] At present, neutral aqueous organic redox flow batteries (AORFBs) mainly include viologen derivatives, quinone molecules, ferrocene, TEMPO compounds, and oxazine compounds. These organic molecules have rich structures and excellent scalability, and are potential electrolyte materials for neutral organic liquid flow batteries. However, these small organic molecules have poor stability when used as electrolytes, and most of them only involve single electron transfer during redox reaction, which greatly limits the improvement of battery energy density and service life. SUMMARY

[0005] In order to overcome the above-mentioned defects of the prior art, the purpose of the present application is to provide a kind of sulfur-containing group element viologen derivative and its preparation method and application in liquid flow battery system, to solve the technical problems that the stability of the prior art small organic molecules as electrolyte is poor, and only involves single electron transfer, thereby limiting the energy density and service life of the battery.

[0006] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0007] The present application discloses a kind of sulfur-containing group element viologen derivative, the structural formula of the sulfur-containing group element viologen derivative is as follows:

[0008]

[0009] In the formula, the value range of n is 1-10;

[0010] R is -OH, -COOH, -PO3 2- , -SO3 - Or -N (Me) 3 + ;

[0011] E is sulfur, selenium, tellurium or bismuth;

[0012] X is Cl, Br or I.

[0013] The present application also discloses a kind of preparation method of the above-mentioned sulfur-containing group element viologen derivative, comprising:

[0014] Under the protection of inert gas, precursor and X-(CH2)n-R are stirred in organic solvent at 95-105 DEG C for 70-80 h to prepare sulfur-containing group element viologen derivative;

[0015] The structure formula of the precursor is as follows:

[0016]

[0017] In the formula, E is sulfur, selenium, tellurium or bismuth;

[0018] X-(CH2)n-R, n is 1-10;

[0019] R is -OH, -COOH, -PO3 2- , -SO3 - or -N(Me)3 + ;

[0020] X is Cl, Br or I.

[0021] Preferably, the molar ratio of the precursor and X-(CH2)n-R is 1:2.5-1:3.

[0022] Preferably, the organic solvent is N,N-dimethylformamide, 1,4-dioxane, tetrahydrofuran or acetonitrile.

[0023] Preferably, when X-(CH2) n -R, X is Cl, the reaction product is filtered, washed and dried in sequence to obtain the target product.

[0024] Preferably, when X-(CH2) n -R, X is Br or I, ion exchange is needed after obtaining the crude product, and the target product is obtained after conversion to chloride and rotary evaporation.

[0025] Preferably, the synthesis method of the precursor is as follows:

[0026] Under the protection of inert gas, 3,3'-dibromo-4,4'-bipyridine is put into a reactor, an organic solvent is added, n-butyllithium is added at-90 to-80℃, stirring for 60 to 90 minutes, and dichlorodisulfide is added in a molar ratio of bromopyridine to dichlorodisulfide 1:1, and stirred at room temperature for not less than 12 hours. After the reaction is completed, the solvent is removed, and the precursor is prepared by post-treatment.

[0027] Further preferably, the organic solvent is tetrahydrofuran.

[0028] The application also discloses application of the sulfur family element-containing viologen derivative in preparation of a flow battery.

[0029] Preferably, the sulfur family element-containing viologen derivative is used as an anode electrolyte material in the flow battery.

[0030] Compared with the prior art, the application has the following beneficial effects:

[0031] The application discloses a kind of sulfur group element viologen derivatives, the conjugation degree of molecular structure is enhanced to some extent by the introduction of sulfur group element, the stability of radical cation state is increased, so that the following properties of the compound are obtained: first, more stable radical state;Second, narrower band gap width, stronger visible light absorption;Third, lower reduction potential, LUMO energy level is very low.At the same time, by introducing various side chain groups, the molecular size is increased, and the solubility of the molecule in water and the stability of the battery are improved.Therefore, the sulfur group element viologen derivative of the application can effectively solve the technical problems that the stability of the existing organic small molecules (such as viologen) used as electrolyte is poor, and only involves single electron transfer, thereby limiting the energy density and service life of the battery.

[0032] The application further discloses a synthesis method of the above-mentioned sulfur group element viologen derivative, which is simple, fast, low in cost and high in product yield.The anode of the water-based organic redox flow battery uses the reversible redox reaction, good electrochemical reversibility and good stability of the bipyridine compound, so that a high-energy-density water-based organic flow battery can be obtained.

[0033] The application further discloses an application of the above-mentioned sulfur group element viologen derivative.The anode electrolyte prepared from the molecule has stable cycle performance in the flow battery system, enriches the types of anode electrolyte of the neutral water-based organic flow battery, and promotes the development of the flow battery in the energy storage field.Through experiments, it is found that the flow battery system has higher advantages in battery capacity, stability, energy density, power density, permeability and service life, and the like.Therefore, the water-based organic flow battery of the sulfur group element viologen derivative has the advantages of flexible power energy design, low cost and scaleable assembly application, and is very suitable for large-scale energy storage applications. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 The cyclic charge-discharge curve diagram of 0.1M [(NPr)2SV]Cl4 (6mL) / 0.1M FcNCl (15mL) prepared for the embodiment 1 in 2M sodium chloride aqueous solution (referred to as 0.1M [(NPr)2SV]Cl4 / FcCNl system) is shown in the following figure.

[0035] Figure 2 The battery stability test diagram of 0.1M [(NPr)2V]Cl4 (6mL) / 0.1M FcNCl (15mL) prepared for the embodiment 1 in 2M sodium chloride aqueous solution is shown in the following figure.

[0036] Figure 3 The cyclic voltammetry test diagram of 0.1M [(NPr)2SV]Cl4 prepared for the embodiment 1 is shown in the following figure.

[0037] Figure 4 Cyclic voltammogram of 0.1 M [(NPr)2SV]Cl4 with FcNCl prepared for Example 1 of the present application. DETAILED DESCRIPTION

[0038] In order to make the personnel in the art better understand the present application, the technical solutions in the embodiments of the present application will be described clearly and completely below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by the person of ordinary skill in the art without making creative labor should belong to the scope of protection of the present application.

[0039] It should be noted that the terms "first", "second" and the like in the specification and claims of the present application and the above-described drawings are used to distinguish similar objects, and do not necessarily indicate a specific order or a chronological sequence. It should be understood that the data thus used can be interchanged under appropriate circumstances, so that the embodiments of the present application described herein can be implemented in an order other than those illustrated or described herein. In addition, the terms "include" and "have" and any variations thereof are intended to cover non-exclusive inclusion, for example, a process, method, system, product or device including a series of steps or units does not have to be limited to those steps or units clearly listed, but can include other steps or units not clearly listed or inherent to these processes, methods, products or devices.

[0040] The present application will be described in further detail below in conjunction with the drawings:

[0041] I. Preparation of sulfur-containing bipyridine

[0042] The sulfur-containing bipyridine can be prepared by the following reaction equation:

[0043]

[0044] wherein E is one of S, Se, Te, Bi.

[0045] As a preferred embodiment, the sulfur-containing bipyridine is selected.

[0046] Preferably, under the protection of inert gas, 3,3'-dibromo-4,4'-bipyridine is put into a reactor, a solvent is added, n-butyllithium is added at -85°C, stirring is carried out for 60-90 minutes, disulfide dichloride is added in a molar ratio of 3,3'-dibromo-4,4'-bipyridine to disulfide dichloride of 1:1, and stirring is carried out at room temperature for more than 12 hours.

[0047] Preferably, the organic solvent used is tetrahydrofuran (THF).

[0048] After the reaction, the solvent was removed by distillation under reduced pressure, and distilled water, 28% ammonia water, and saturated ammonium chloride aqueous solution were added in sequence, and then extracted with chloroform for 2-3 times. The lower organic phase was taken, anhydrous sodium sulfate was added to remove residual water, and then filtered. The product was purified by column chromatography, and then the solvent was removed by distillation under reduced pressure to obtain the sulfur-containing dipyridine.

[0049] II. Preparation of the sulfur-containing group element viologen anode electrolyte material

[0050] Prepared by the following reaction equation steps:

[0051]

[0052] wherein the substituent R is any one of -OH, -COOH, -PO3 2- , -SO3 - , -N(Me)3 + ; n represents the length of the alkyl chain, and the value range is 1-10; X is one of Cl, Br, and I.

[0053] As one of the preferred embodiments, the precursor is selected to be sulfur-containing dipyridine; X-(CH2) n -R is preferably (3-bromopropyl)trimethylammonium bromide.

[0054] Under the protection of inert gas, the precursor and X-(CH2) n -R are put into a reaction container in an equivalent ratio of 1:2.5, an organic solvent is added, and then stirred at 100°C for 72h.

[0055] Preferably, the organic solvent is DMF.

[0056] After the reaction, cooled to room temperature. When X in X-(CH2) n -R is Cl, the mixture is suction filtered, and then the solid is washed with cold DMF, MeCN and ether in sequence, and then dried in vacuum.

[0057] When X in X-(CH2) n -R is Br or I, the mixture is suction filtered, and then the solid is washed with cold DMF, MeCN and ether in sequence, and then dried in vacuum. After the obtained crude product is completely dissolved in water, column anion exchange is performed with Amberlite IRA-900 chloride-forming anion exchange resin, and then water is removed to obtain a solid.

[0058] The application will be further described in detail in combination with specific embodiments and drawings:

[0059] Example 1

[0060] The sulfur-containing bipyridine prepared by the present application is prepared by the following steps:

[0061] A clean 200 mL flask is prepared (baked in an oven at 110°C for not less than 2 hours before use), 3,3'-dibromo-4,4'-bipyridine (623 mg, 2.0 mmol) is added under inert gas protection, 50 mL of tetrahydrofuran is added as a solvent and stirred. A low-temperature reactor is used to reduce the reaction temperature to -85°C, and n-butyllithium (1.68 mL, 4.2 mmol) is slowly added dropwise under this condition. After stirring for one hour at -85°C, bisulfur dichloride (284 mg, 2.1 mmol) is added, the temperature is raised to room temperature, and the reaction is carried out for not less than 12 hours. After the reaction is completed, the solvent is distilled off under reduced pressure. 30 mL of distilled water, 15 mL of ammonia water (28%), and 15 mL of saturated ammonium chloride aqueous solution are added in sequence, and stirred thoroughly. Trichloromethane is used for extraction for 2-3 times, each time 30 mL, and the lower organic phase is taken out, anhydrous sodium sulfate is added to remove residual water, and filtered. The filtrate is purified by column chromatography to obtain the sulfur-containing bipyridine.

[0062] The sulfur-containing viologen anode electrolyte material [(NPr)2SV]Cl4 prepared by the present application is prepared by the following steps:

[0063] A clean 250 mL Schlenk flask is prepared under anhydrous and anaerobic conditions, SV (1 g, 5.94 mmol) and (3-bromopropyl)trimethylammonium bromide (3.88 g, 14.86 mmol) are mixed with 40 mL of DMF, and stirred at 100°C for 3 days. After the reaction is completed, it is cooled to room temperature, filtered, and washed with 3×10 mL of cold DMF and 3×10 mL of acetone in sequence, and dried in a vacuum drying oven at 50°C. The crude product is placed in a beaker and water is added until it is completely dissolved, and the product is dissolved in water and extracted with chloroform. IRA-900 chloride is formed into an anion exchange resin, column anion exchange is carried out, water is removed by reduced pressure distillation, and the obtained white solid is [(NPr)2V]Cl4. 2.84 g, the yield is about 90%. 1 H NMR (400 MHz, D2O) δ 10.06 (s, 2H), 9.25 (d, J = 6.6 Hz, 2H), 9.16 (d, J = 6.6 Hz, 2H), 5.03 (t, J = 7.7 Hz, 4H), 3.63-3.58 (m, 4H), 3.18 (s, 18H), 2.78-2.70 (m, 4H). 13 C NMR (101 MHz, D2O) δ 143.67, 143.31, 142.89, 139.61, 124.07, 62.41, 59.32, 53.26, 24.93. HRMS (ESI) m / z: [M-3Cl] + calcd for C22 H 36 N4S129.4215;found 129.4202.

[0064] Example 2

[0065] The prepared chalcogen-containing viologen anode electrolyte material [(C3OH)2SV]Cl2of the present application is prepared by the following steps:

[0066] A clean 250 mL Schlenk flask is prepared under anhydrous and anaerobic conditions, SV (1 g, 5.94 mmol) is mixed with 3-bromo, 1-propanol (2.65 g, 14.86 mmol) and 40 mL of DMF, and stirred at 100°C for 3d. After the reaction is completed, it is cooled to room temperature, filtered, washed with 3x10 mL of cold DMF, 3x10 mL of acetone, and dried in a vacuum oven at 50°C. The crude product is placed in a beaker and water is added until it is completely dissolved. The product is filtered and dried in a vacuum oven at 50°C. IRA-900 chloride-forming anion exchange resin is used for column anion exchange, and water is removed by vacuum distillation. The obtained white solid is [(C3OH)2SV]Cl2.

[0067] Example 3

[0068] The prepared chalcogen-containing viologen anode electrolyte material [(C3PO(OH)2)2SV]Cl2of the present application is prepared by the following steps:

[0069] A clean 250 mL Schlenk flask is prepared under anhydrous and anaerobic conditions, SV (1 g, 5.94 mmol) is mixed with diethyl (3-bromopropyl) phosphonate (3.85 g, 14.86 mmol) and 40 mL of DMF, and stirred at 100°C for 3d. After the reaction is completed, it is cooled to room temperature, filtered, washed with 3x10 mL of cold DMF, 3x10 mL of acetone, and dried in a vacuum oven at 50°C. The crude product is placed in a beaker and water is added until it is completely dissolved. The product is filtered and dried in a vacuum oven at 50°C. IRA-900 chloride-forming anion exchange resin is used for column anion exchange, and water is removed by vacuum distillation. The obtained white solid is [(C3PO(OH)2)2SV]Cl2.

[0070] Example 4

[0071] The prepared chalcogen-containing viologen anode electrolyte material [(C3OCH3)2SV]Cl2of the present application is prepared by the following steps:

[0072] A clean 250 mL Schlenk flask was prepared under anhydrous and anaerobic conditions, and SV (1 g, 5.94 mmol) was mixed with 1-bromo-3-methoxypropane (2.28 g, 14.86 mmol) and 40 mL of DMF, and stirred at 100°C for 3 days. After the reaction was completed, it was cooled to room temperature, filtered, washed with 3x10 mL of cold DMF, 3x10 mL of acetone, and dried in a vacuum oven at 50°C. The crude product was placed in a beaker and water was added until it was completely dissolved. The product was filtered and dried in a vacuum oven at 50°C. IRA-900 chloride was used to form an anion exchange resin for column anion exchange, and water was removed by distillation under reduced pressure. The white solid obtained was [(C3OCH3)2SV]Cl2.

[0073] Example 5

[0074] The sulfur-containing viologen anode electrolyte material [(C3COOH)2SV]Cl2 prepared in the present application was prepared by the following steps:

[0075] A clean 250 mL Schlenk flask was prepared under anhydrous and anaerobic conditions, and SV (1 g, 5.94 mmol) was mixed with 1-bromo-3-methoxypropane (2.28 g, 14.86 mmol) and 40 mL of DMF, and stirred at 100°C for 3 days. After the reaction was completed, it was cooled to room temperature, filtered, washed with 3x10 mL of cold DMF, 3x10 mL of acetone, and dried in a vacuum oven at 50°C. The crude product was placed in a beaker and water was added until it was completely dissolved. The product was filtered and dried in a vacuum oven at 50°C. IRA-900 chloride was used to form an anion exchange resin for column anion exchange, and water was removed by distillation under reduced pressure. The white solid obtained was [(C3OCH3)2SV]Cl2.

[0076] Third, the application of a sulfur-containing viologen anode electrolyte material

[0077] The sulfur-containing viologen derivative prepared in Example 2 was used to prepare a neutral aqueous organic redox flow battery electrode material, which can be prepared by the following steps:

[0078] Step 1: Assemble the core clamp

[0079] The neutral aqueous organic redox flow battery used for testing has a single cell structure, and the positive end plate, positive insulating plate, positive conductive plate, positive flow frame, positive graphite felt, positive gasket, anion exchange membrane, negative gasket, negative graphite felt, negative flow frame, negative conductive plate, negative insulating plate, and negative end plate are sequentially fixed with bolts, connected with external pipelines, and checked for looseness. If loose, it can be tightened again. Before testing, the sealing and pressure test should be performed. On the basis of the above-mentioned clamp, two liquid storage bottles and a peristaltic pump are connected. After 2h circulation, if there is no leakage and no change in liquid volume, it can be stored for standby. If the above-mentioned defects occur, it needs to be adjusted again.

[0080] Step two: preparation of electrode material,

[0081] A sufficient amount of 2M NaCl solution is prepared in a volumetric flask, and a ferrocene solution is used as the cathode electrolyte, with the chemical formula Fe(C5H5)2 and the English name Ferrocene, which is also called ferrocene (FcNCl).

[0082] Preparation of 0.1M [(NPr)2SV]Cl4 / 0.1M FcNCl

[0083] 372mg of [(NPr)2SV]Cl4 and 280mg of FcNCl are dissolved in 6mL and 15mL of 2M NaCl solution respectively, and stirred or ultrasonicated to completely dissolve them. The concentration of both in the NaCl solution is 0.1M. The volume ratio between the mixture formed by the two is 1:2.5 to ensure that [(NPr)2SV]Cl4 is fully charged and discharged. Bubble with Ar for 10 minutes. The derivative [(NPr)2SV]Cl4 and FcNCl are used as the anode electrolyte and cathode electrolyte of the battery respectively, and are referred to as 0.1M [(NPr)2SV]Cl4 / 0.1M FcNCl.

[0084] Step three: assembly of neutral aqueous organic redox flow battery and performance test;

[0085] The clamp prepared in step one and the solution of step two are placed in a glove box, and the prepared [(NPr)2SV]Cl4 solution is used as the anode electrolyte and the FcNCl solution is used as the cathode electrolyte. Connect the external power supply, peristaltic pump, and new Wei tester, set the program, and perform the charge and discharge test.

[0086] After the above steps, the basic test data of the prepared 0.1M [(NPr)2SV]Cl4 / 0.1M FcNCl system are as follows: voltage range 0.1-1.25V, current density 40mA / cm 2Cycling 5000 cycles, capacity retention: 96.72%, capacity attenuation: 0.00066% / cycle, time: 282.12h, time dependence: 0.01% / h, battery capacity 10.57mAh, overall capacity utilization 65.73%.

[0087] Therefore, the above battery test proves that the viologen derivative containing sulfur family elements is an excellent anode electrolyte material in the neutral aqueous redox flow battery. The introduction of quaternary ammonium salt not only can effectively improve the water solubility, but also can increase the molecular size, improve the stability of the battery, and the planar structure of the conjugate makes them have a narrow band gap, fast dynamic characteristics. In the AORFB system of 0.1M[(NPr)2SV]Cl4 / 0.1M FcNCl, good stability is shown, -OHPr, -COOH, -SO3 - or-PO3 2 -hydrophilic groups can also be used to modify the structure of the molecule, further improve the solubility, and obtain more excellent anode electrolyte materials.

[0088] The present application carries out relevant tests on the above-mentioned embodiment of the sulfur family element-containing viologen anode electrolyte material, and the test results are shown in Figures 1-4 :

[0089] From Figure 1 it can be seen that when the anode electrolyte is 6ml 0.1M[(NPr)2SV]Cl4 and the cathode electrolyte is 9ml 0.1M FcNCl, the capacity retention rate can reach 96.72% after 5000 cycles, and the coulombic efficiency is close to 100%.

[0090] From Figure 2 it can be seen that the voltage range of the 0.1M[(NPr)2SV]Cl4 / FcNCl redox flow battery is 0.1V-1.25V, and the discharge capacity is 10.57mAh

[0091] From Figure 3 it can be seen that within the measured voltage range, the anode electrolyte [(NPr)2SV]Cl4 has two redox peaks, and the positions of the two redox peaks are E 1 1 / 2 =-0.29V and E 2 1 / 2 =-0.75V.

[0092] From Figure 4 it can be seen that when the anode electrolyte is [(NPr)2SV]Cl4 (the positions of the two redox peaks are E 1 1 / 2When the anode electrolyte is FcNCl (the redox peak position E = 0.61 V) and the cathode electrolyte is FcNCl (the redox peak position E = -0.29 V), the full cell voltage can reach 0.9 V when single electron transfer occurs.

[0093] The above merely illustrates the technical idea of the present application and cannot limit the protection scope of the present application. Any modification made according to the technical idea of the present application on the basis of the technical scheme falls within the protection scope of the present application.

Claims

1. A chalcogen-containing viologen derivative, characterized by, The structural formula of the sulfur-containing group element viologen derivative is as follows: 。 2. The method for producing a sulfur family element-containing viologen derivative according to claim 1, characterized by, The application further relates to a sulfur-containing group element viologen derivative prepared by the method. Under the protection of inert gas, sulfur-containing bipyridine and (3-bromopropyl) trimethylammonium bromide are stirred and reacted in an organic solvent at 95-105 DEG C for 70-80 hours; after the reaction is completed, the mixture is cooled to room temperature, the solid is extracted by suction filtration, and then is washed with cold DMF, MeCN and ether in sequence, and then is dried in vacuum to obtain a crude product; the crude product is completely dissolved in water, and then is subjected to column anion exchange with Amberlite IRA-900 chloride-forming anion exchange resin, and then is spun to remove water to obtain the target product, i.e. the sulfur-containing group element viologen derivative. The mass ratio of the sulfur-containing bipyridine to (3-bromopropyl) trimethylammonium bromide is 1:3.

88. The structural formula of the sulfur-containing bipyridine is as follows: wherein E is sulfur.

3. The method for preparing a sulfur family element-containing viologen derivative according to claim 2, characterized by, The organic solvent is N, N-dimethylformamide, 1, 4-dioxane, tetrahydrofuran or acetonitrile.

4. The method for preparing a sulfur family element-containing viologen derivative according to claim 2, characterized by, The synthesis method of the sulfur-containing bipyridine is as follows: Under the protection of inert gas, 3, 3'-dibromo-4, 4'-bipyridine is put into a reactor, an organic solvent is added, and then n-butyllithium is added at-90~-80 DEG C, and is stirred for 60-90 minutes; according to the molar ratio of bromopyridine to dichlorodisulfide 1:1, dichlorodisulfide is added, and is stirred at room temperature for not less than 12 hours; after the reaction is completed, the solvent is removed, and the sulfur-containing bipyridine is prepared through post-treatment.

5. The method for preparing a sulfur family element-containing viologen derivative according to claim 4, characterized by, The organic solvent is tetrahydrofuran.

6. Use of the sulfur-containing group element viologen derivative in claim 1 in the preparation of an anode electrolyte material of a flow battery.

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