A battery cathode containing small organic molecules with carboxyl groups, an aqueous zinc-organic battery and methods for preparing both

Abstract

The application provides a battery positive electrode containing an organic small molecule containing a carboxyl group, a water-based zinc-organic battery and preparation methods of both. The method for preparing the battery positive electrode comprises the following steps: first, 4,4',4'',4'''-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoic acid, a graphite conductive agent and a polytetrafluoroethylene binder are weighed according to the mass ratio, put into a mortar, N-methyl pyrrolidone is added, uniformly ground and then coated on a current collector, and then the battery positive electrode is obtained after drying treatment. 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 a water-based zinc-organic battery. Since the raw material organic small molecule used contains a carboxyl group, the prepared 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.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of chemical power sources, and particularly relates to a battery positive electrode containing an organic small molecule with a carboxyl group, a water-based zinc-organic battery, and a preparation method of both. BACKGROUND

[0002] To alleviate the limitations of intermittent renewable energy and promote its more effective integration into large-scale power grids, zinc ion batteries have attracted much attention in the field of large-scale energy storage due to their remarkable advantages such as environmental friendliness, high theoretical capacity, high safety, and low cost. Although Zn 2+ ions have been widely studied as typical charge carriers in zinc ion batteries, their large hydration structure and high desolvation energy barrier often hinder the migration of interfacial charges.

[0003] In contrast, non-metallic ions (such as H + , NH4 + , Cl - , OH - ) with light mass and small hydration structure exhibit fast desolvation processes and migration kinetics. In particular, H + ions, with the smallest mass and hydration structure, can achieve fast reaction kinetics, thereby providing excellent energy storage; and NH4 + ions with a tetrahedral structure can form flexible hydrogen bonds with active sites in the positive electrode material, effectively stabilizing the discharge product and prolonging the cycle life of the battery. Given the complementarity of H + and NH4 + ions in structure and function, the co-storage of both is expected to overcome the barriers of kinetics and stability, achieving fast and persistent zinc storage.

[0004] To fully exploit the potential of non-metallic H + / NH4 + ions, it is crucial to rationally design positive electrode materials that match them to enhance the performance of energy storage devices. Organic small molecules, with their unique advantages such as abundant resources, diverse structures, and adjustable functions, are gradually becoming promising positive electrode candidates in the field of water-based zinc-organic batteries.

[0005] Benefiting from 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 low active site density of imine small molecules and their less-than-ideal frontier molecular orbital energy levels inevitably limit the capacity of the battery. At the same time, the high solubility of organic small molecules in water-based electrolytes often leads to irreversible capacity loss during battery cycling.

[0006] In order to effectively solve these problems, grafting a homogeneous electron-withdrawing group (such as -COOH) to the structure of an imine small molecule can effectively adjust the electronic structure and electrochemical activity of the imine small molecule, and promote its electron delocalization and redox kinetics.

[0007] Therefore, there is an urgent need to design high-density active organic positive electrode materials containing novel redox groups to further improve battery performance. SUMMARY

[0008] The present application is to solve the above problems, and aims to provide a battery positive electrode containing a carboxyl group, a water-based zinc-organic battery, and a preparation method of both.

[0009] The present application provides a preparation method of a battery positive electrode containing a carboxyl group, which is characterized by using 4,4',4'',4'''-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoic acid organic small molecules to prepare, comprising the following steps: step S1, taking 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 into a mortar, and add N-methyl pyrrolidone in the mortar, after uniform grinding, get mixed slurry; step S2, uniformly coat the mixed slurry on the current collector, and then put it into a vacuum oven, and get the battery positive electrode after drying treatment.

[0010] The preparation method of the battery positive electrode containing a carboxyl group provided by the present application can also have the following characteristics: 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 preparation method of the battery positive electrode containing a carboxyl group provided by the present application can 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 when drying treatment is performed, the temperature in the vacuum oven is 70-90℃, and the drying time is 10-15 h.

[0012] The present application provides a battery positive electrode containing a carboxyl group, which is characterized by: being prepared by any one of the above preparation methods of a battery positive electrode containing a carboxyl group.

[0013] The application provides a water-based zinc-organic battery, characterized in that the battery anode contains the organic small molecule containing a carboxyl group of the application.

[0014] The water-based zinc-organic battery provided by the application can also have the following characteristics: the battery anode is a zinc foil, the zinc content of the zinc foil is greater than or equal to 99.99%, the electrolyte is any one or more of the aqueous solutions of NH4BF4, NH4CF3SO3, NH4Cl, (NH4)2SO4 and Zn(BF4)2, the concentration of the electrolyte is 1 mol / L to 10 mol / L, the diaphragm is filter paper or glass fiber, and the battery shell is a CR2032 type button cell shell. -1 -1

[0015] The water-based zinc-organic battery provided by the application can also have the following characteristics: the method for preparing the water-based zinc-organic battery comprises the following steps: step one, placing a diaphragm between the battery anode and the battery cathode, and then placing the diaphragm in the battery shell after finishing the arrangement; and step two, adding an electrolyte into the battery shell to obtain the water-based zinc-organic battery.

[0016] Effects of the application

[0017] According to the battery anode containing an organic small molecule containing a carboxyl group, the water-based zinc-organic battery and the preparation methods of both, the battery anode containing an organic small molecule containing a carboxyl group is prepared first, and then the water-based zinc-organic battery is assembled using the prepared battery anode. In the process of the electrochemical reaction of the water-based zinc-organic battery prepared by the application, when the organic small molecule of 4,4', 4'', 4'''-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoic acid is used as the anode active material of the water-based zinc-organic battery, the abundant carboxyl groups can not only serve as redox active sites to significantly improve the capacity of the battery, but also effectively regulate the electronic structure of the organic small molecule, significantly improve the electrical conductivity and energy band structure of the molecule, and reduce the energy barrier of the redox reaction, which is conducive to better charge transfer efficiency and lower kinetic hindrance, so as to promote the redox reaction. The presence of the carboxyl group enables the organic small molecule of 4,4', 4'', 4'''-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoic acid to overcome the slow interfacial charge transfer of Zn 2+ ions due to the high desolvation energy barrier, effectively reduce the charge transport energy barrier, and thus effectively improve the charge transfer efficiency of the battery and the capacity of the battery. + + ​​​The charge carrier preferentially coordinates, not only realizes fast redox (de) coordination kinetics, but also can initiate hydrogen bond chemical action, forms a stable hydrogen bond (N-H…N) bridged discharge product, and the assembled battery exhibits high specific capacity storage performance, high specific capacity, energy density and superior cycle stability, and the cycle life of the battery is also significantly improved.

[0018] In addition, the main raw materials used in the present application have a wide source, low cost and environmental friendliness, the whole system electrode and electrolyte preparation process is carried out at normal temperature and pressure, the operation is simple, safe and pollution-free. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 is the conductivity graph of the 4,4',4'',4'''-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoic acid organic small molecule in embodiment one of the present application;

[0020] Figure 2 is the band gap graph of the 4,4',4'',4'''-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoic acid organic small molecule in embodiment one of the present application;

[0021] Figure 3 is the rate performance graph of the aqueous zinc-organic battery assembled in embodiment three of the present application;

[0022] Figure 4 is the cycle stability graph of the aqueous zinc-organic battery assembled in embodiment three of the present application at a current density of 5A / g;

[0023] Figure 5 is the rate performance graph of the aqueous zinc-organic battery assembled in embodiment four of the present application;

[0024] Figure 6 is the rate performance graph of the aqueous zinc-organic battery assembled in embodiment five of the present application;

[0025] Figure 7 is the cycle stability graph of the aqueous zinc-organic battery assembled in embodiment five of the present application at a current density of 5A / g. DETAILED DESCRIPTION

[0026] In order to make the technical means, creative features, purposes and effects realized by the present application easy to understand, the following embodiments combine the drawings to specifically describe the battery anode of an organic small molecule containing a carboxyl group, the aqueous zinc-organic battery and the preparation methods thereof.

[0027] <Embodiment one>

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

[0029] In step one, 4,4', 4'', 4'''-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoic acid, a graphite conductive agent and a polytetrafluoroethylene binder are weighed according to the mass ratio and put into a mortar, N-methyl pyrrolidone is added into the mortar, and the mixture is uniformly ground for 25-35 min to obtain a mixed slurry, and in the embodiment, the specific experimental process is as follows:

[0030] In step one, 4,4', 4'', 4'''-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoic acid, a graphite conductive agent and a polytetrafluoroethylene binder are weighed according to the mass ratio and put into a mortar, N-methyl pyrrolidone is added into the mortar, and the mixture is uniformly ground for 25-35 min to obtain a mixed slurry, and in the embodiment, the specific experimental process is as follows:

[0031] In step two, the mixed slurry is uniformly coated on any one or more current collectors selected from the group consisting of titanium foil, nickel mesh, titanium mesh, stainless steel mesh and carbon paper, and then placed into a vacuum oven, the temperature of the vacuum oven is set to 70-90 DEG C, and the mixed slurry is dried for 10-15 h to obtain the battery positive electrode, and in the embodiment, the specific experimental process is as follows:

[0032] In step two, the mixed slurry is uniformly coated on any one or more current collectors selected from the group consisting of titanium foil, nickel mesh, titanium mesh, stainless steel mesh and carbon paper, and then placed into a vacuum oven, the temperature of the vacuum oven is set to 70-90 DEG C, and the mixed slurry is dried for 10-15 h to obtain the battery positive electrode, and in the embodiment, the specific experimental process is as follows:

[0033] Figure 1 The conductivity diagram of the 4,4', 4'', 4'''-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoic acid organic small molecule used in the embodiment one of the application is shown in the figure.

[0034] As shown in the figure, Figure 1 the 4,4', 4'', 4'''-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoic acid organic small molecule used in the embodiment one has a high conductivity of 7.2*10 -8 S cm -1 , which is beneficial to better charge transfer efficiency and lower kinetic hindrance to promote redox reaction.

[0035] Figure 2 The band gap diagram of the 4,4', 4'', 4'''-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoic acid organic small molecule used in the embodiment one of the application is shown in the figure.

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

[0037] <Embodiment Two>

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

[0039] Step one, according to the mass ratio, 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoate, graphite conductive agent and polytetrafluoroethylene binder are weighed and put into a mortar, and N-methyl pyrrolidone is added in the mortar, and the mixture is uniformly ground for 25-35 min to obtain a mixed slurry. In this embodiment, the specific experimental process is as follows:

[0040] According to the mass ratio of 6:3:1, 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoate organic small molecule, graphite conductive agent and polytetrafluoroethylene binder are put into a mortar, and N-methyl pyrrolidone is added in the mortar, and the mixture is uniformly ground for 30 min to obtain a mixed slurry.

[0041] Step two, the mixed slurry is uniformly coated on any one or more current collectors of titanium foil, nickel mesh, titanium mesh, stainless steel mesh and carbon paper, and then placed in a vacuum oven, the temperature of the vacuum oven is set to 70-90℃, and the mixed slurry is dried for 10-15h to obtain a battery positive electrode. In this embodiment, the specific experimental process is as follows:

[0042] The mixed slurry is uniformly coated on the titanium foil current collector with a diameter of 1.2 cm with a blade, and then placed in an 80℃ vacuum oven for drying treatment for 12h to obtain an electrode sheet to be assembled as a battery positive electrode.

[0043] <Embodiment Three>

[0044] The embodiment provides a water-based zinc-organic battery containing a battery positive electrode containing a carboxyl group organic small molecule prepared in embodiment one and a preparation method thereof, the preparation method comprising the following steps:

[0045] Step one, place filter paper or glass fiber diaphragm between the battery positive electrode and the battery negative electrode, and then place it in 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 the positive electrode, and the negative electrode is zinc foil with a zinc content of ≥99.99%. A GE-Whatman glass fiber separator is placed between the positive and negative electrodes. After being arranged, the battery is placed in a CR2032 button battery case.

[0047] Step two, add a 1 mol L solution to the battery casing. -1 ~10mol L -1 An aqueous zinc-organic battery is obtained by assembling any one or more of the aqueous solutions of NH4BF4, NH4CF3SO3, NH4Cl, (NH4)2SO4, and Zn(BF4)2. In this embodiment, the specific experimental procedure is as follows:

[0048] Adding 2M NH4BF4 electrolyte to the CR2032 button cell casing, an aqueous zinc-organic battery is assembled.

[0049] <Example 4>

[0050] This embodiment provides an aqueous zinc-organic battery and its preparation method. The aqueous zinc-organic battery contains a battery cathode containing small organic molecules with carboxyl groups prepared in Example 2. The preparation method includes the following steps:

[0051] Step one: Place filter paper or glass fiber membrane between the positive and negative terminals of the battery, arrange it properly, and then place it into the battery casing. In this embodiment, the specific experimental procedure is as follows:

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

[0053] Step two, add a 1 mol L solution to the battery casing. -1 ~10mol L -1 An aqueous zinc-organic battery is obtained by assembling any one or more of the aqueous solutions of NH4BF4, NH4CF3SO3, NH4Cl, (NH4)2SO4, and Zn(BF4)2. In this embodiment, the specific experimental procedure is as follows:

[0054] Adding 3M NH4BF4 electrolyte to the CR2032 button cell casing, an aqueous zinc-organic battery is assembled.

[0055] <Example 5>

[0056] This embodiment provides an aqueous zinc-organic battery and its preparation method. The aqueous zinc-organic battery contains a battery cathode with small organic molecules containing carboxyl groups prepared in Example 1. The preparation method includes the following steps:

[0057] Step one: Place filter paper or glass fiber membrane between the positive and negative terminals of the battery, arrange it properly, and then place it into the battery casing. In this embodiment, the specific experimental procedure is as follows:

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

[0059] Step two, add a 1 mol L solution to the battery casing. -1 ~10mol L -1 An aqueous zinc-organic battery is obtained by assembling any one or more of the aqueous solutions of NH4BF4, NH4CF3SO3, NH4Cl, (NH4)2SO4, and Zn(BF4)2. In this embodiment, the specific experimental procedure is as follows:

[0060] Adding 2M Zn(BF4)2 electrolyte to the CR2032 button cell casing, an aqueous zinc-organic battery is assembled.

[0061] <Experiment Example 1>

[0062] In this experimental example, the electrochemical performance of the aqueous zinc-organic battery prepared in Example 3 was tested, including: testing the energy storage performance of the device using a CHI660E electrochemical workstation; and conducting cycle and rate performance tests 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 Embodiment 3 of the present invention.

[0064] like Figure 3 As shown, the aqueous zinc-organic battery prepared in this Example 3 has a specific capacity of 290 mAh g when charged and discharged at 0.5 A / g. -1 Above, the rate capacity reaches 140mAh g when charged and discharged at 20A / g. -1 The above demonstrates 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 5A / g.

[0066] like Figure 4 As shown, the zinc-organic battery assembled in Example 3 retained 85.9% of its capacity after 20,000 charge-discharge cycles, demonstrating excellent cycle stability.

[0067] <Experimental Example Two>

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

[0069] Figure 5 is a rate performance graph of the water-based zinc-organic battery assembled in Example Four of the present application.

[0070] As shown in Figure 5 , the zinc-organic battery prepared in Example Four had a specific capacity of 290mAh g -1 above when charged and discharged at 0.5A / g, a rate capacity of 140mAh g -1 above when charged and discharged at 20A / g, and exhibited high specific capacity storage performance.

[0071] <Experimental Example Three>

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

[0073] Figure 6 is a rate performance graph of the water-based zinc-organic battery assembled in Example Five of the present application.

[0074] As shown in Figure 6 , the zinc-organic battery prepared in Example Five had a specific capacity of 150mAh g -1 , a rate capacity of 31mAh g -1 above when charged and discharged at 20A / g, and exhibited poor specific capacity storage performance.

[0075] Figure 7 is a cycle stability graph of the water-based zinc-organic battery assembled in Example Five of the present application at a current density of 5A / g.

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

[0077] The performance test results of the zinc-organic batteries prepared by using different electrolytes in Example 3 and Example 5 show that the cycle stability (85.9%) of the 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoate organic small molecule positive electrode in the NH4BF4 aqueous electrolyte is significantly better than the cycle stability (17.8%) in the Zn(BF4)2 aqueous electrolyte. Obviously, the 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoate organic small molecule positive electrode and Zn 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, thereby leading to the solvation of Zn 2+ The ion reaction energy barrier is too high and the interface charge transfer kinetics is slow, which finally causes the zinc-organic battery to exhibit poor cycle stability.

[0078] Effects of the embodiments

[0079] According to the battery positive electrode containing a carboxyl group, the aqueous zinc-organic battery and the preparation methods of both according to the embodiments of the present application, the battery positive electrode containing a carboxyl group is prepared first, and the aqueous zinc-organic battery is assembled using the prepared battery positive electrode. The aqueous zinc-organic battery prepared by the embodiments of the present application can overcome the slow interface charge transfer of Zn 2+ ions caused by the high desolvation energy barrier, effectively reduces the charge transfer energy barrier, and thus the 4,4',4",4"'-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoate organic small molecule as the positive electrode active material of the aqueous zinc-organic battery can be oxidized and reduced (desolvation) at a high speed. + / H + The charge carriers preferentially coordinate, not only realizing fast oxidation and reduction (desolvation) coordination kinetics, but also triggering hydrogen bond chemical action to form a stable hydrogen bond (N-H…N) bridged discharge product. The assembled battery exhibits high specific capacity storage performance, high specific capacity, energy density and superior cycle stability, and the cycle life of the battery is also significantly improved.

[0080] In addition, the main raw materials used in the present application have a wide source, low cost and are environmentally friendly. The whole system electrode and electrolyte preparation process is carried out at normal temperature and pressure, which is simple to operate, safe and pollution-free.

[0081] In addition, the performance test results of zinc-organic batteries prepared by different electrolytes show that the carboxyl / imine functional groups in the 4,4',4'',4'''-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetrayl) tetrabenzoic acid organic small molecule used in the preparation of the aqueous zinc-organic battery in the embodiment of the present application preferentially react with high-kinetic non-metal NH4 + / H + The coordination reaction of the charge carrier not only realizes fast redox (de) coordination kinetics, significantly improves the battery capacity, but also effectively inhibits the dissolution of the discharge product, and improves the cycle life of the battery.

[0082] The above-mentioned embodiments are preferred cases of the present application and are not used to limit the protection scope of the present application.

Claims

1. A method for preparing a battery cathode containing a small organic molecule with a carboxyl group, characterized in that, The organic small molecule 4,4',4'',4'''-(pyrazino[2,3-g]quinoxaline-2,3,7,8-tetramethyl)tetrabenzoic acid was prepared using the following steps: Step S1: Weigh the 4, 4', 4'', 4'''-(pyrazino[2, 3-g]quinoxaline-2, 3, 7, 8-tetramethyl)tetrabenzoic acid, graphite conductive agent and polytetrafluoroethylene binder according to the mass ratio, put them into a mortar, add N-methylpyrrolidone to the mortar, grind evenly to obtain a mixed slurry; Step S2: The mixed slurry is uniformly coated onto the current collector, and then placed in a vacuum oven for drying to obtain the battery positive electrode.

2. The method for preparing the battery cathode containing a carboxyl group of small organic molecules 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-tetramethyl)tetrabenzoic acid, the graphite conductive agent, and the polytetrafluoroethylene adhesive is (6~7):(3~2):

1. The grinding time is 25~35 minutes.

3. The method for preparing the battery cathode containing a carboxyl group of small organic molecules 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 diameter of the current collector is 1-1.5 cm. During the drying process, the temperature in the vacuum oven is 70~90℃, and the drying time is 10~15h.

4. A battery positive electrode containing a small organic molecule with a carboxyl group, characterized in that: It is prepared using the method for preparing a battery cathode containing a small organic molecule with a carboxyl group as described in any one of claims 1-3.

5. An aqueous zinc-organic battery, characterized in that: A battery cathode containing the small organic molecules containing carboxyl groups as described in claim 4.

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

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 foil has a zinc content of ≥99.99%. The electrolyte is any one or more of the following: aqueous solutions of NH4BF4, NH4CF3SO3, NH4Cl, (NH4)2SO4, and Zn(BF4)2. The concentration of the electrolyte is 1 mol / L. −1 ~10 mol L −1 , The diaphragm is filter paper or glass fiber. The battery casing is a CR2032 button-type battery casing.

8. The aqueous zinc-organic battery according to claim 7, characterized in that, The method for preparing the aqueous zinc-organic battery includes the following steps: Step 1: Place the separator between the positive and negative terminals of the battery, arrange it properly, and then put it into the battery casing. Step 2: Add the electrolyte into the battery casing and assemble the aqueous zinc-organic battery.

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