Battery positive electrode of small organic molecule containing carboxyl group, aqueous zinc-organic battery and preparation methods of battery positive electrode and aqueous zinc-organic battery

Abstract

The invention provides a carboxyl group-containing small organic molecule battery positive electrode, an aqueous zinc-organic battery and preparation methods of the battery positive electrode and the aqueous zinc-organic battery. The preparation method of the battery positive electrode comprises the following steps: firstly, weighing 4, 4 ', 4' ', 4 '''-(pyrazino [2, 3-g] quinoxaline-2, 3, 7, 8-tetrayl) tetrabenzoic acid, the graphite conductive agent and the polytetrafluoroethylene adhesive according to the mass ratio, putting into a mortar, then adding N-methyl pyrrolidone, uniformly grinding, coating on a current collector, and then drying to obtain the battery positive electrode. The obtained battery positive electrode is used as a positive electrode, a zinc foil is used as a negative electrode, an electrolyte and a battery shell are assembled together to prepare the aqueous zinc-organic battery, and the used raw material organic small molecules contain carboxyl groups, so that the prepared battery shows high specific capacity storage performance, high specific capacity, high energy density and excellent cycling stability; and the cycle life of the battery is also remarkably prolonged.

Description

Technical Field

[0001] The invention belongs to the technical field of chemical power sources, and specifically relates to a battery positive electrode of an organic small molecule containing a carboxyl group, an aqueous zinc-organic battery, and a preparation method of the two. Background Art

[0002] In order to alleviate the limitations of intermittent renewable energy and promote its more efficient integration into large-scale power grids, zinc-ion batteries have attracted much attention in the field of large-scale energy storage due to their significant advantages such as environmental friendliness, high theoretical capacity, high safety and low cost. 2+ Zn-ion ions have been extensively studied as typical charge carriers in Zn-ion batteries, but their large hydrated structures and high desolvation barriers usually hinder the migration of interfacial charges.

[0003] In contrast, non-metallic ions with light weight and small hydrated structures (such as H + NH4 + , Cl - OH - ) exhibited rapid desolvation and migration kinetics. In particular, H + ions, with their minimal mass and hydrated structure, enable fast reaction kinetics, thus providing excellent energy storage; while NH4 + ions can coordinate with the active sites in the positive electrode material to form flexible hydrogen bonds, effectively stabilizing the discharge products and thus extending the cycle life of the battery. + and NH4 + Due to the structural and functional complementarity of the ions, the co-storage of the two is expected to break through the kinetic and stability barriers and achieve rapid and long-lasting zinc storage.

[0004] In order to fully explore the non-metallic H + / NH4 + The potential of ions, the rational design of the cathode material that matches it is crucial to improve the performance of energy storage devices. Organic small molecules are gradually becoming a highly promising cathode candidate material in the field of aqueous zinc-organic batteries due to their unique advantages such as abundant resources, diverse structures and adjustable functions.

[0005] Thanks to the lone pair of electrons on the nitrogen atom, imine small molecules containing C=N groups usually have high redox activity, excellent electrochemical reversibility and fast reaction kinetics. However, the active site density of imine small molecules is low and their frontier molecular orbital energy levels are not ideal, which inevitably limits the capacity of the battery. At the same time, the high solubility of organic small molecules in aqueous electrolytes often leads to irreversible capacity loss during battery cycling.

[0006] In order to effectively solve these problems, homogeneous electron-withdrawing groups (such as -COOH) are grafted into the structure of imine small molecules, which can effectively regulate the electronic structure and electrochemical activity of imine small molecules and promote their electron delocalization and redox kinetics.

[0007] Therefore, there is an urgent need to design high-density active organic cathode materials containing new redox groups to further improve battery performance. Summary of the invention

[0008] The present invention is made to solve the above problems, and aims to provide a battery positive electrode of organic small molecules containing carboxyl groups, an aqueous zinc-organic battery and a preparation method of the two.

[0009] The invention provides a method for preparing a battery positive electrode of an organic small molecule containing a carboxyl group, characterized in that the method is prepared by using an organic small molecule of 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid, and comprises the following steps: step S1, weighing 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid, a graphite conductive agent and a polytetrafluoroethylene adhesive according to a mass ratio, putting them into a mortar, adding N-methylpyrrolidone into the mortar, and uniformly grinding to obtain a mixed slurry; step S2, uniformly coating the mixed slurry on a current collector, and then putting the mixed slurry into a vacuum oven, and drying the mixed slurry to obtain a battery positive electrode.

[0010] The method for preparing a battery positive electrode of an organic small molecule containing a carboxyl group provided by the present invention may also have the following characteristics: wherein, in step S1, the mass ratio of 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid, graphite conductive agent and polytetrafluoroethylene binder is (6-7):(3-2):1, and the grinding time is 25-35 min.

[0011] The method for preparing a battery positive electrode of an organic small molecule containing a carboxyl group provided by the present invention may also have the following characteristics: in step S2, the current collector is any one or more of titanium foil, nickel mesh, titanium mesh, stainless steel mesh, and carbon paper, the area of ​​the current collector is 1-1.5 cm, the current collector is titanium foil, and during the drying process, the temperature in the vacuum oven is 70-90° C., and the drying time is 10-15 h.

[0012] The present invention provides a battery positive electrode of an organic small molecule containing a carboxyl group, which is characterized in that it is prepared by using any one of the above methods for preparing a battery positive electrode of an organic small molecule containing a carboxyl group.

[0013] The invention provides an aqueous zinc-organic battery, characterized in that the battery positive electrode contains the organic small molecule containing a carboxyl group of the invention.

[0014] The aqueous zinc-organic battery provided by the present invention may also have the following characteristics: the negative electrode of the battery is a zinc foil, the zinc content of the zinc foil is ≥99.99%, the electrolyte is any one or more of NH4BF4, NH4CF3SO3, NH4Cl, (NH4)2SO4, and an aqueous solution of Zn(BF4)2, and the concentration of the electrolyte is 1 mol L -1 ~10mol L -1 The diaphragm is filter paper or glass fiber, and the battery shell model is CR2032 button type battery shell.

[0015] The aqueous zinc-organic battery provided by the present invention may also have the following characteristics: the method for preparing the aqueous zinc-organic battery comprises the following steps: step 1, placing a separator between the positive electrode and the negative electrode of the battery, and placing it in a battery shell after arranging; step 2, adding an electrolyte into the battery shell, and assembling to obtain an aqueous zinc-organic battery.

[0016] Functions and Effects of the Invention

[0017] According to the present invention, a battery positive electrode of an organic small molecule containing a carboxyl group, an aqueous zinc-organic battery and a preparation method of the two, a battery positive electrode of an organic small molecule containing a carboxyl group is first prepared, and the prepared battery positive electrode is used to assemble an aqueous zinc-organic battery. In the electrochemical reaction process of the aqueous zinc-organic battery prepared by the present invention, when the 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid organic small molecule is used as the positive electrode active material of the aqueous zinc-organic battery, its abundant carboxyl groups can not only serve as redox active sites, significantly improving the capacity of the battery; but also effectively regulating the electronic structure of the organic small molecule, significantly improving the electrical conductivity and energy band structure of the molecule, and reducing the energy barrier of the redox reaction, which is conducive to better charge transfer efficiency and lower kinetic hindrance to promote the redox reaction. The presence of the carboxyl group enables the 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid organic small molecule to overcome the Zn 2+ The slow interfacial charge transfer caused by the high desolvation energy barrier of ions effectively reduces the charge transfer energy barrier, thereby reacting with NH4 + / H +The preferential coordination of charge carriers not only achieves fast redox (de)coordination kinetics, but also triggers hydrogen bonding chemistry to form stable hydrogen-bonded (NH…N)-bridged discharge products. The assembled battery exhibits high specific capacity storage performance, high specific capacity, energy density and excellent cycle stability, and the cycle life of the battery is also significantly improved.

[0018] In addition, the main raw materials used in the present invention are widely available, low-cost and environmentally friendly. The entire system electrode and electrolyte preparation process is carried out at room temperature and pressure, which is simple to operate, safe and pollution-free. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is the conductivity diagram of the organic small molecule 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid in Example 1 of the present invention;

[0020] Figure 2 is the energy band gap diagram of the organic small molecule 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid in Example 1 of the present invention;

[0021] Figure 3 is a rate performance diagram of the aqueous zinc-organic battery assembled in Example 3 of the present invention;

[0022] Figure 4 is a cycle stability diagram of the aqueous zinc-organic battery assembled in Example 3 of the present invention at a current density of 5 A / g;

[0023] Figure 5 is a rate performance diagram of the aqueous zinc-organic battery assembled in Example 4 of the present invention;

[0024] Figure 6 is a rate performance diagram of the aqueous zinc-organic battery assembled in Example 5 of the present invention;

[0025] Figure 7 This is a cycle stability diagram of the aqueous zinc-organic battery assembled in Example 5 of the present invention at a current density of 5 A / g. DETAILED DESCRIPTION

[0026] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the following examples and drawings specifically describe a battery positive electrode of an organic small molecule containing a carboxyl group, an aqueous zinc-organic battery and a preparation method of the two of the present invention.

[0027] <Example 1>

[0028] This embodiment provides a battery positive electrode of an organic small molecule containing a carboxyl group and a preparation method thereof, the preparation method comprising the following steps:

[0029] Step 1: weigh 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid, graphite conductive agent and polytetrafluoroethylene binder according to the mass ratio, put them into a mortar, add N-methylpyrrolidone into the mortar, and grind evenly for 25 to 35 minutes to obtain a mixed slurry. In this embodiment, the specific experimental process is as follows:

[0030] 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid organic small molecule, graphite conductive agent and polytetrafluoroethylene adhesive were weighed into a mortar in a mass ratio of 7:2:1, and N-methylpyrrolidone was added to the mortar and then uniformly ground for 30 minutes to obtain a mixed slurry.

[0031] Step 2: evenly coat the mixed slurry on any one or more current collectors of titanium foil, nickel mesh, titanium mesh, stainless steel mesh, and carbon paper, and then put it into a vacuum oven. The temperature of the vacuum oven is set to 70-90° C. After drying for 10-15 hours, the positive electrode of the battery is obtained. In this embodiment, the specific experimental process is as follows:

[0032] The mixed slurry was evenly coated on a titanium foil current collector with a diameter of 1.2 cm using a blade, and dried in a vacuum oven at 80° C. for 12 h to obtain an electrode sheet to be assembled as a battery positive electrode.

[0033] Figure 1 This is the conductivity diagram of the organic small molecule 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid used in Example 1 of the present invention.

[0034] like Figure 1 As shown, the organic small molecule 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid used in this Example 1 has a molecular weight of 7.2×10 -8 S cm -1 The high electrical conductivity is conducive to better charge transfer efficiency and lower kinetic hindrance to promote redox reactions.

[0035] Figure 2 This is the energy band gap diagram of the organic small molecule 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid used in Example 1 of the present invention.

[0036] like Figure 2As shown, the 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid organic small molecule used in this embodiment has an ultra-low band gap of 2.14 eV, which is much lower than most organic electrode materials, indicating that the organic small molecule has high electrical conductivity and can promote fast reaction kinetics.

[0037] <Example 2>

[0038] This embodiment provides a battery positive electrode of an organic small molecule containing a carboxyl group and a preparation method thereof, the preparation method comprising the following steps:

[0039] Step 1: weigh 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid, graphite conductive agent and polytetrafluoroethylene binder according to the mass ratio, put them into a mortar, add N-methylpyrrolidone into the mortar, and grind evenly for 25 to 35 minutes to obtain a mixed slurry. In this embodiment, the specific experimental process is as follows:

[0040] 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid organic small molecule, graphite conductive agent and polytetrafluoroethylene adhesive were weighed into a mortar in a mass ratio of 6:3:1, and N-methylpyrrolidone was added to the mortar and then uniformly ground for 30 minutes to obtain a mixed slurry.

[0041] Step 2: evenly coat the mixed slurry on any one or more current collectors of titanium foil, nickel mesh, titanium mesh, stainless steel mesh, and carbon paper, and then put it into a vacuum oven. The temperature of the vacuum oven is set to 70-90° C. After drying for 10-15 hours, the positive electrode of the battery is obtained. In this embodiment, the specific experimental process is as follows:

[0042] The mixed slurry was evenly coated on a titanium foil current collector with a diameter of 1.2 cm using a blade, and dried in a vacuum oven at 80° C. for 12 h to obtain an electrode sheet to be assembled as a battery positive electrode.

[0043] <Example 3>

[0044] This embodiment provides an aqueous zinc-organic battery and a preparation method thereof. The aqueous zinc-organic battery contains a battery positive electrode of an organic small molecule containing a carboxyl group prepared in Example 1. The preparation method comprises the following steps:

[0045] Step 1: Place filter paper or glass fiber separator between the positive electrode and the negative electrode of the battery, and put it into the battery shell after arranging. In this embodiment, the specific experimental process is as follows:

[0046] The positive electrode of the battery prepared in Example 1 is used as the positive electrode, the zinc foil with a zinc content of ≥99.99% is used as the negative electrode, a GE-Whatman glass fiber separator is placed between the positive and negative electrodes, and after being arranged, it is placed in a CR2032 button battery shell.

[0047] Step 2: Add 1 mol L -1 ~10mol L -1 Any one or more of NH4BF4, NH4CF3SO3, NH4Cl, (NH4)2SO4, and Zn(BF4)2 aqueous solutions are assembled to obtain an aqueous zinc-organic battery. In this embodiment, the specific experimental process is as follows:

[0048] 2M NH4BF4 electrolyte was added into the CR2032 button battery shell to assemble an aqueous zinc-organic battery.

[0049] <Example 4>

[0050] This embodiment provides an aqueous zinc-organic battery and a preparation method thereof. The aqueous zinc-organic battery contains a battery positive electrode of an organic small molecule containing a carboxyl group prepared in Example 2. The preparation method comprises the following steps:

[0051] Step 1: Place filter paper or glass fiber separator between the positive electrode and the negative electrode of the battery, and put it into the battery shell after arranging. In this embodiment, the specific experimental process is as follows:

[0052] The positive electrode of the battery prepared in Example 2 is used as the positive electrode, the zinc foil with a zinc content of ≥99.99% is used as the negative electrode, a GE-Whatman glass fiber separator is placed between the positive and negative electrodes, and after being arranged, it is placed in a CR2032 button battery shell.

[0053] Step 2: Add 1 mol L -1 ~10mol L -1 Any one or more of NH4BF4, NH4CF3SO3, NH4Cl, (NH4)2SO4, and Zn(BF4)2 aqueous solutions are assembled to obtain an aqueous zinc-organic battery. In this embodiment, the specific experimental process is as follows:

[0054] 3M NH4BF4 electrolyte was added into the CR2032 button battery shell to assemble an aqueous zinc-organic battery.

[0055] <Example 5>

[0056] This embodiment provides an aqueous zinc-organic battery and a preparation method thereof. The aqueous zinc-organic battery contains a battery positive electrode of an organic small molecule containing a carboxyl group prepared in Example 1. The preparation method comprises the following steps:

[0057] Step 1: Place filter paper or glass fiber separator between the positive electrode and the negative electrode of the battery, and put it into the battery shell after arranging. In this embodiment, the specific experimental process is as follows:

[0058] The positive electrode of the battery prepared in Example 1 is used as the positive electrode, the zinc foil with a zinc content of ≥99.99% is used as the negative electrode, a GE-Whatman glass fiber separator is placed between the positive and negative electrodes, and after being arranged, it is placed in a CR2032 button battery shell.

[0059] Step 2: Add 1 mol L -1 ~10mol L -1 Any one or more of NH4BF4, NH4CF3SO3, NH4Cl, (NH4)2SO4, and Zn(BF4)2 aqueous solutions are assembled to obtain an aqueous zinc-organic battery. In this embodiment, the specific experimental process is as follows:

[0060] 2M Zn(BF4)2 electrolyte was added to the CR2032 button battery shell to assemble an aqueous zinc-organic battery.

[0061] <Experimental Example 1>

[0062] In this experimental example, the aqueous zinc-organic battery prepared in Example 3 was subjected to electrochemical performance testing, including: testing the device energy storage performance by a CHI660E electrochemical workstation. Cycling and rate performance tests were performed on a LAND CT2001A battery testing system. The voltage window was 0-1.8V.

[0063] Figure 3 This is a rate performance diagram of the aqueous zinc-organic battery assembled in Example 3 of the present invention.

[0064] like Figure 3 As shown in FIG. 3 , the specific capacity of the aqueous zinc-organic battery prepared in Example 3 is 290 mAh g when charged and discharged at 0.5 A / g. -1 When charging and discharging at 20A / g, the rate capacity reaches 140mAh g -1 The above shows high specific capacity storage performance.

[0065] Figure 4 This is a cycle stability diagram of the aqueous zinc-organic battery assembled in Example 3 of the present invention at a current density of 5 A / g.

[0066] like Figure 4 As shown, the capacity retention rate of the zinc-organic battery assembled in Example 3 after 20,000 cycles of charge and discharge is 85.9%, which has excellent cycle stability.

[0067] <Experimental Example 2>

[0068] In this experimental example, the aqueous zinc-organic battery prepared in Example 4 was subjected to electrochemical performance testing, including: testing the device energy storage performance using a CHI660E electrochemical workstation. Cycling and rate performance tests were performed on a LAND CT2001A battery testing system. The voltage window was 0-1.8V.

[0069] Figure 5 This is a rate performance diagram of the aqueous zinc-organic battery assembled in Example 4 of the present invention.

[0070] like Figure 5 As shown in the figure, the specific capacity of the zinc-organic battery prepared in Example 4 is 290 mAh g when charged and discharged at 0.5 A / g. -1 When charging and discharging at 20A / g, the rate capacity reaches 140mAh g -1 The above shows high specific capacity storage performance.

[0071] <Experimental Example 3>

[0072] In this experimental example, the aqueous zinc-organic battery prepared in Example 5 was subjected to electrochemical performance testing, including: testing the device energy storage performance through a CHI660E electrochemical workstation. Cycling and rate performance tests were performed on a LAND CT2001A battery testing system. The voltage window was 0-1.8V.

[0073] Figure 6 This is a rate performance diagram of the aqueous zinc-organic battery assembled in Example 5 of the present invention.

[0074] like Figure 6 As shown, the specific capacity of the zinc-organic battery prepared in Example 5 is 150 mAh g when charged and discharged at 0.5 A / g. -1 When charged and discharged at 20A / g, the rate capacity is 31mAh g -1 , showing poor specific capacity storage performance.

[0075] Figure 7 This is a cycle stability diagram of the aqueous zinc-organic battery assembled in Example 5 of the present invention at a current density of 5 A / g.

[0076] like Figure 7 As shown, the capacity retention rate of the zinc-organic battery assembled in Example 5 after 20,000 cycles of charge and discharge is 17.8%, and the cycle stability is poor.

[0077] By comparing the performance test results of the zinc-organic battery prepared using different electrolytes in Example 3 and Example 5, it can be seen that the cycle stability of the organic small molecule positive electrode of 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid in NH4BF4 aqueous electrolyte (85.9%) is significantly better than that in Zn(BF4)2 aqueous electrolyte (17.8%). Obviously, the organic small molecule positive electrode of 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid has a better cycling stability than that in Zn(BF4)2 aqueous electrolyte (17.8%). 2+ When the ions are coordinated, a rigid chemical bond is formed, which cannot inhibit the dissolution of the discharge product in the aqueous Zn(BF4)2 electrolyte, resulting in the solvated Zn 2+ The high ionic reaction energy barrier and sluggish interfacial charge transfer kinetics ultimately lead to poor cycling stability of zinc-organic batteries.

[0078] Functions and Effects of the Embodiments

[0079] According to the battery positive electrode of an organic small molecule containing a carboxyl group, an aqueous zinc-organic battery and a preparation method of the two involved in the embodiment of the present invention, a battery positive electrode of an organic small molecule containing a carboxyl group is first prepared, and the prepared battery positive electrode is used to assemble an aqueous zinc-organic battery. In the electrochemical reaction process of the aqueous zinc-organic battery prepared by the embodiment of the present invention, when the organic small molecule 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid is used as the positive electrode active material of the aqueous zinc-organic battery, it can overcome the Zn 2+ The slow interfacial charge transfer caused by the high desolvation energy barrier of ions effectively reduces the charge transfer energy barrier, thereby reacting with NH4 + / H + The preferential coordination of charge carriers not only achieves fast redox (de)coordination kinetics, but also triggers hydrogen bonding chemistry to form stable hydrogen-bonded (NH…N)-bridged discharge products. The assembled battery exhibits high specific capacity storage performance, high specific capacity, energy density and excellent cycle stability, and the cycle life of the battery is also significantly improved.

[0080] In addition, the main raw materials used in the present invention are widely available, low-cost and environmentally friendly. The entire system electrode and electrolyte preparation process is carried out at room temperature and pressure, which is simple to operate, safe and pollution-free.

[0081] In addition, the performance test results of the zinc-organic battery prepared by different electrolytes in the embodiments of the present invention show that the carboxyl / imine functional groups in the organic small molecule 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid used in the aqueous zinc-organic battery prepared in the embodiments of the present invention preferentially bind to the highly kinetic non-metallic NH4 + / H + The coordination reaction of charge carriers not only achieves rapid redox (de)coordination kinetics, significantly improving the battery capacity, but also effectively inhibits the dissolution of discharge products and improves the battery cycle life.

[0082] The above-mentioned embodiments are preferred examples of the present invention and are not intended to limit the protection scope of the present invention.

Claims

1. A method for preparing a battery positive electrode of an organic small molecule containing a carboxyl group, characterized in that: The method is prepared by using 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid organic small molecule, comprising the following steps: Step S1, weighing the 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid, graphite conductive agent and polytetrafluoroethylene binder according to the mass ratio, putting them into a mortar, adding N-methylpyrrolidone into the mortar, and uniformly grinding to obtain a mixed slurry; Step S2, uniformly coating the mixed slurry on the current collector, and then placing it in a vacuum oven, and obtaining a battery positive electrode after drying.

2. The method for preparing a positive electrode of a battery containing an organic small molecule having a carboxyl group according to claim 1, characterized in that: in, In step S1, the mass ratio of the 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl)tetrabenzoic acid, the graphite conductive agent and the polytetrafluoroethylene binder is (6-7): (3-2): 1, The grinding time is 25 to 35 minutes.

3. The method for preparing a positive electrode of a battery containing an organic small molecule having a carboxyl group according to claim 1, characterized in that: in, In step S2, the current collector is any one or more of titanium foil, nickel mesh, titanium mesh, stainless steel mesh, and carbon paper. The area of ​​the current collector is 1-1.5 cm, The current collector is titanium foil, During the drying process, the temperature in the vacuum oven is 70 to 90° C. and the drying time is 10 to 15 hours.

4. A battery positive electrode of an organic small molecule containing a carboxyl group, characterized in that: The battery positive electrode is prepared by the method for preparing a battery positive electrode of an organic small molecule containing a carboxyl group as described in any one of claims 1 to 3.

5. An aqueous zinc-organic battery, characterized in that: A battery positive electrode comprising the organic small molecule containing a carboxyl group as claimed in claim 3.

6. The aqueous zinc-organic battery according to claim 5, characterized in that: in, The aqueous zinc-organic battery comprises the battery positive electrode, the battery negative electrode, a separator, an electrolyte and a battery shell.

7. The aqueous zinc-organic battery according to claim 6, characterized in that: in, The negative electrode of the battery is zinc foil, The zinc content of the zinc foil is ≥99.99%, The electrolyte is any one or more of NH4BF4, NH4CF3SO3, NH4Cl, (NH4)2SO4, and Zn(BF4)2 aqueous solutions. The concentration of the electrolyte is 1 mol L -1 ~10mol L -1 , The diaphragm is filter paper or glass fiber, The model of the battery shell is a CR2032 button-type battery shell.

8. The aqueous zinc-organic battery according to claim 7, characterized in that: The method for preparing the aqueous zinc-organic battery comprises the following steps: Step 1, placing the separator between the positive electrode of the battery and the negative electrode of the battery, and putting it into the battery shell after arranging; Step 2: adding the electrolyte into the battery shell to assemble the aqueous zinc-organic battery.

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