Porous nonmetal organic framework material, preparation method thereof and aqueous zinc-iodine battery

Abstract

The invention relates to the technical field of aqueous batteries, in particular to a porous non-metal organic framework material, a preparation method thereof and an aqueous zinc-iodine battery, and the preparation method comprises the following steps: mixing organic amine with an organic solvent, mixing the obtained organic amine solution with an inorganic acid solution, and stirring to obtain the porous non-metal organic framework material. Organic amine cations and inorganic acid anions are combined to form metal-free closely-packed ionic clusters, a porous organic halogenated ammonium salt framework material is formed, and the iodine loading capacity of a host can be further improved based on high porosity and large specific surface area of a non-metal organic framework material; due to interaction between nitrogen-containing active sites of the porous non-metal organic framework material and iodine, the shuttle diffusion effect of polyiodide ions can be effectively inhibited, the mutual conversion rate of iodine is improved, reaction kinetics of iodine is accelerated, coulombic efficiency and cycling stability of the zinc-iodine energy storage battery are remarkably improved, self-discharge of the zinc-iodine energy storage battery is inhibited, and specific capacity fading is reduced.

Description

Technical Field

[0001] This invention relates to the field of aqueous battery technology, and in particular to a porous non-metallic organic framework material, its preparation method, and its application. Background Technology

[0002] Aqueous secondary batteries, using highly conductive, non-flammable aqueous solutions as electrolytes, exhibit excellent high power output and safety, making them a focus of attention in green energy storage. In recent years, aqueous zinc metal batteries have gained attention due to their high specific capacity (820 Ah kg / m³). -1 and 5854Ah L -1 Iodine, with its low oxidation potential (-0.76V vs. SHE) and strong chemical stability, has become a new development direction for advanced energy storage. Iodine also possesses advantages such as high safety, abundant reserves, low cost, and environmental friendliness, and boasts a high theoretical capacity (211 mAh g / g). -1 This makes zinc-iodine energy storage batteries demonstrate enormous potential commercial value. Iodine, as a cathode, mainly faces challenges such as poor intrinsic conductivity, slow reaction kinetics, and the presence of soluble polyiodide ions (I3). - I5 - Problems such as shuttle dissolution and limited bulk iodine load lead to severe self-discharge, low coulombic efficiency and energy efficiency, and poor cycle stability in zinc-iodine batteries, thus limiting their commercial application.

[0003] Currently, carbon-based materials are the primary cathode materials used as iodine-loaded hosts. However, the loading capacity of carbon-based materials for iodine is limited, and the simple physical adsorption between iodine and carbon-based materials leads to slow reaction kinetics of elemental iodine and polyiodide ion shuttle, resulting in decreased coulombic efficiency and reduced cycle life of the battery. Therefore, it is essential to research and develop iodine-loaded cathode materials with high conductivity, strong loading capacity, and high conversion efficiency in order to suppress polyiodide ion shuttle diffusion and accelerate iodine reaction kinetics during zinc-iodine battery energy storage.

[0004] Therefore, existing technologies still need to be improved and developed. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a porous non-metallic organic framework material, its preparation method and application, in order to solve the problems of poor conductivity, low iodine loading, low specific capacity and poor cycle stability of existing zinc-iodine energy storage battery cathode materials.

[0006] The technical solution of the present invention is as follows: A method for preparing a porous nonmetallic organic framework material includes the following steps: An organic amine is mixed with an organic solvent to obtain an organic amine solution; The organic amine solution and the inorganic acid solution are mixed and stirred to obtain a porous non-metallic organic framework material.

[0007] The method for preparing the porous non-metallic organic framework material, wherein the organic amine is selected from one or more of 1,3,5-tris(4-aminophenyl)benzene, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, and 4',4''',4''''-(1,3,5-triazine-2,4,6-triyl)tris(([1,1'-biphenyl]-4-amine)).

[0008] The method for preparing the porous non-metallic organic framework material, wherein the concentration of the organic amine solution is greater than or equal to 5 mg / mL.

[0009] The method for preparing the porous non-metallic organic framework material, wherein the organic solvent is selected from one or more of acetone, dichloromethane, hexafluoroisopropanol, methanol, ethyl acetate, chlorobenzene, 1,4-dioxane, methyltetrahydrofuran, and tetrahydrofuran.

[0010] The method for preparing the porous non-metallic organic framework material, wherein the inorganic acid is one or more of hydrogen chloride methanol solution and hydrogen bromide aqueous solution.

[0011] A porous non-metallic organic framework material is prepared using the preparation method of the porous non-metallic organic framework material.

[0012] The porous non-metallic organic framework material is, in particular, one of the following: an amino halide of 1,3,5-tris(4-aminophenyl)benzene and chlorine, an amino halide of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine and bromine, and an amino halide of 4',4''',4'''''-(1,3,5-triazine-2,4,6-triyl)tri(([1,1'-biphenyl]-4-amine)) and chlorine.

[0013] An aqueous zinc-iodine battery includes a positive electrode sheet; the positive electrode sheet includes a current collector, a positive electrode active layer disposed on the surface of the current collector, and iodine element loaded on the positive electrode active layer; the positive electrode active layer contains the porous non-metallic organic framework material.

[0014] The aqueous zinc-iodine battery, wherein the positive electrode active layer further contains conductive additives and binders; the mass ratio of the porous non-metallic organic framework material, the conductive additives and the binders is (6-7):(2-3):1.

[0015] In the aqueous zinc-iodine battery, the conductive additive is selected from one or more of Ketjen black, acetylene black, and carbon black; the binder is selected from one or more of polyvinylidene fluoride, polytetrafluoroethylene, and hydroxymethyl cellulose; and the current collector is selected from one of carbon cloth, carbon paper, titanium mesh, and titanium foil.

[0016] Beneficial Effects: This invention provides a porous non-metallic organic framework material and its preparation method, as well as an aqueous zinc-iodine battery. The preparation method of the porous non-metallic organic framework material includes the following steps: mixing an organic amine with an organic solvent to obtain an organic amine solution; mixing the organic amine solution with an inorganic acid solution and stirring to obtain a porous non-metallic organic framework material (N-MOFs). This invention forms a porous organic ammonium halide framework material by combining organic amine cations with inorganic acid anions to form metal-free, tightly packed ion clusters. Based on the high porosity and large specific surface area of ​​the non-metallic organic framework material, the iodine loading capacity of the host can be improved. Due to the interaction between the nitrogen-containing active sites of the porous non-metallic organic framework material and iodine, the polyiodide ion shuttle diffusion effect can be effectively suppressed, improving the iodine interconversion rate while accelerating the iodine reaction kinetics, thereby significantly improving the coulombic efficiency and cycle stability of the zinc-iodine energy storage battery, and suppressing its self-discharge to reduce specific capacity decay. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the process flow for preparing a porous non-metallic organic framework material according to the present invention; Figure 2 This is a synthetic route diagram of the porous non-metallic organic framework material TAPT.Cl in Example 1; Figure 3 The image shows the XRD pattern of the porous non-metallic organic framework material TAPT.Cl in Example 1. Figure 4 This is a charge-discharge curve of the aqueous zinc-iodine battery in Example 1 for different number of cycles; Figure 5 The graph shows the coulombic efficiency test results of the aqueous zinc-iodine battery in Example 1 during the cycling process. Detailed Implementation

[0018] This invention provides a porous non-metallic organic framework material and its preparation method, as well as an aqueous zinc-iodine battery. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0019] It will be understood by those skilled in the art that, unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It should also be understood that terms such as those defined in general dictionaries should be understood to have the same meaning as in the context of the prior art, and should not be interpreted in an idealized or overly formal sense unless specifically defined as herein.

[0020] like Figure 1 As shown, the present invention provides a method for preparing a porous non-metallic organic framework material, comprising the following steps: Step S10: Mix the organic amine with an organic solvent to obtain an organic amine solution; Step S20: The organic amine solution and the inorganic acid solution are mixed and stirred to obtain a porous non-metallic organic framework material.

[0021] In this embodiment, organic amine cations and inorganic acid anions combine to form metal-free, tightly packed ion clusters, forming a porous organic halide ammonium salt framework material. Based on the high porosity and large specific surface area of ​​the non-metallic organic framework material, the host's iodine loading capacity can be improved. Due to the interaction between the nitrogen-containing active sites of the porous non-metallic organic framework material and iodine, the polyiodide ion shuttle diffusion effect can be effectively suppressed, the iodine interconversion rate can be improved, and the iodine reaction kinetics can be accelerated, thereby significantly improving the coulombic efficiency and cycle stability of the zinc-iodine energy storage battery, and suppressing its self-discharge to reduce specific capacity decay.

[0022] Specifically, the preparation method can synthesize porous non-metallic organic framework amino halide salt materials with thermodynamic stability, tunable pore structure, and high porosity. Unlike traditional metal-organic frameworks (MOFs) based on regularity, this material crystallizes using a unique method where organic amines act as cations and inorganic acids act as anions to form halide salts. The nodes in these porous non-metallic organic framework amino halide salts are metal-free, tightly packed ion clusters formed by the combination of cations and anions. The application of this non-metallic organic framework material powder in aqueous zinc-iodine batteries can effectively improve the loading capacity of optimized electrode material carriers for iodine. Based on the fact that this material contains multiple nitrogen-containing active sites, it accelerates the reaction kinetics of iodine and improves the interconversion of iodine, thereby significantly improving the coulombic efficiency and cycle stability of zinc-iodine energy storage batteries and suppressing their self-discharge to reduce specific capacity decay.

[0023] In some embodiments, the organic amine is selected from one or more of 1,3,5-tris(4-aminophenyl)benzene (TAPT), 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TT), and 4',4''',4''''-(1,3,5-triazine-2,4,6-triyl)tri(([1,1'-biphenyl]-4-amine)) (TTBT). The above-mentioned organic amines can provide organic amine cations for porous non-metallic organic framework materials, which combine with inorganic acid anions to form metal-free, closely packed ionic clusters, thus forming porous organic ammonium halide framework materials.

[0024] In some embodiments, the concentration of the organic amine solution is greater than or equal to 5 mg / mL. Providing an organic amine solution with a concentration greater than or equal to 5 mg / mL can accelerate the nucleation rate of nonmetallic organic frameworks and is beneficial for controlling the pore structure of nonmetallic organic framework materials.

[0025] In a preferred embodiment, the concentration of the organic amine solution is 5 mg / mL.

[0026] In some embodiments, the organic solvent is selected from one or more of acetone, dichloromethane, hexafluoroisopropanol, methanol, ethyl acetate, chlorobenzene, 1,4-dioxane, methyltetrahydrofuran, and tetrahydrofuran. These organic solvents can better dissolve organic amines, providing a uniformly dispersed organic amine solution.

[0027] In some embodiments, the inorganic acid is one or more of hydrogen chloride methanol solution and hydrogen bromide aqueous solution. The aforementioned inorganic acid can provide inorganic acid anions to porous non-metallic organic framework materials, allowing organic amine cations to combine with inorganic acid anions to form metal-free, closely packed ionic clusters. Preferably, an excess of inorganic acid is added to promote the reaction.

[0028] In some embodiments, the concentration of the hydrogen chloride methanol solution is less than 1.25 M; the concentration of the hydrogen bromide aqueous solution is 30 wt%-48 wt%.

[0029] In a preferred embodiment, the concentration of the hydrogen chloride methanol solution is 1.25 M; and the concentration of the hydrogen bromide aqueous solution is 48 wt%.

[0030] In addition, the present invention also provides a porous non-metallic organic framework material, which is prepared by the preparation method of the porous non-metallic organic framework material.

[0031] In this embodiment, the porous non-metallic organic framework material prepared by the above preparation method combines organic amine cations with inorganic acid anions to form metal-free, tightly packed ion clusters, forming porous organic ammonium halide framework materials (N-MOFs). Based on the high porosity and large specific surface area of ​​the non-metallic organic framework material, the host iodine loading capacity can be improved. Due to the interaction between the nitrogen-containing active sites of the porous non-metallic organic framework material and iodine, the polyiodide ion shuttle diffusion effect can be effectively suppressed, the iodine interconversion rate can be improved, and the iodine reaction kinetics can be accelerated, thereby significantly improving the coulombic efficiency and cycle stability of the zinc-iodine energy storage battery, and suppressing its self-discharge to reduce specific capacity decay.

[0032] In some embodiments, the porous nonmetallic organic framework material is one of the following: 1,3,5-tris(4-aminophenyl)benzene and chlorine amino halide (TAPT.Cl), 2,4,6-tris(4-aminophenyl)-1,3,5-triazine and bromine amino halide (TT.Br), and 4',4''',4'''''-(1,3,5-triazine-2,4,6-triyl)tri(([1,1'-biphenyl]-4-amine)) and chlorine amino halide (TTBT.Cl).

[0033] In addition, the present invention also provides an aqueous zinc-iodine battery, including a positive electrode sheet; the positive electrode sheet includes a current collector, a positive electrode active layer disposed on the surface of the current collector, and iodine element loaded on the positive electrode active layer; the positive electrode active layer contains the porous non-metallic organic framework material.

[0034] In this embodiment, due to the interaction between the nitrogen-containing active sites of the porous non-metallic organic framework material and iodine, the polyiodide ion shuttle diffusion effect can be effectively suppressed, improving the iodine interconversion rate while accelerating the iodine reaction kinetics. This significantly improves the coulombic efficiency and cycle stability of the zinc-iodine energy storage battery, and suppresses its self-discharge, reducing specific capacity decay. Uniformly coating the porous non-metallic organic framework material onto a conductive carbon-based current collector not only enhances the interaction between the carrier material and active iodine in the development and application of zinc-iodine batteries through multiple nitrogen-containing active sites, but also improves the iodine interconversion efficiency and enhances electrochemical reaction kinetics.

[0035] In some embodiments, the positive electrode active layer further comprises conductive additives and binders; the mass ratio of the porous non-metallic organic framework material, the conductive additives and the binders is (6-7):(2-3):1.

[0036] In a preferred embodiment, the mass ratio of the porous non-metallic organic framework material, the conductive additive, and the binder is 6:3:1.

[0037] In some embodiments, the conductive additive is selected from one or more of Ketjen black, acetylene black, and carbon black; the binder is selected from one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and hydroxymethyl cellulose; and the current collector is selected from one of carbon cloth, carbon paper, titanium mesh, and titanium foil.

[0038] In some embodiments, the preparation of the positive electrode sheet includes the following steps: uniformly mixing the porous non-metallic organic framework material, the conductive additive, and the binder with N-methylpyrrolidone (NMP) as a solvent and coating it onto a current collector with a diameter of 10 mm-15 mm, with a coating mass greater than 5 mg; then vacuum drying it at a drying temperature of 40℃-60℃ for no less than 8 hours to obtain a current collector loaded with a positive electrode active layer; finally immersing the current collector loaded with the positive electrode active layer in a 0.5 M zinc iodide solution for 20 min-40 min to achieve active iodine loading, and then vacuum drying it again in an oven to obtain the positive electrode sheet.

[0039] In some embodiments, an active electrode is prepared using the porous non-metallic organic framework material (N-MOFs) provided by the present invention as the positive electrode, a zinc foil as the negative electrode, a glass fiber membrane as the separator, and an aqueous zinc salt solution (zinc trifluoromethanesulfonate or zinc sulfate) as the electrolyte for assembly to obtain an aqueous zinc-iodine battery.

[0040] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention.

[0041] Example 1 This embodiment provides a porous nonmetallic organic framework material TAPT.Cl, the synthesis route of which is shown below. Figure 2 As shown, the porous non-metallic organic framework material TAPT.Cl was also applied to an aqueous zinc-iodine battery, as detailed below: Dissolve 100 mg of organic amine (TAPT) in 20 mL of tetrahydrofuran (THF) to prepare a 5 mg / mL solution. Slowly add excess 1.25 M inorganic acid HCl methanol solution, stir at room temperature for 1 h, centrifuge, wash with an appropriate amount of THF, and dry in a vacuum drying oven at 60 °C for 12 h. Remove from the drying oven and store the obtained sample (porous non-metallic organic framework material TAPT.Cl) in a desiccator for later use.

[0042] A porous non-metallic organic framework material TAPT.Cl, prepared by neutralization of organic amines and inorganic acids, was mixed with Ketjen black and PVDF in a mass ratio of 6:3:1 using NMP as a solvent. The mixture was then uniformly coated onto a 12 mm diameter hydrophilic carbon cloth current collector. The current collector was then dried in a vacuum oven at 60 °C for 12 h. The electrode was then immersed in a 1.0 M ZnI₂ solution for 30 min and dried in a vacuum oven at 40 °C for 12 h, completing the preparation of the iodine-loaded host electrode. The active iodine loading was approximately 8 mg. Using this iodine-loaded positive electrode as the positive electrode, a 1 M ZnSO₄ aqueous solution as the electrolyte, zinc foil as the negative electrode, and a glass fiber membrane as the separator, an aqueous zinc-iodine battery was assembled.

[0043] The aqueous zinc-iodine battery underwent chemical performance testing, and its performance at 1.0 A·g -1 It can release ~140 mAh·g -1 The reversible capacity. XRD analysis results of the porous nonmetallic organic framework material TAPT.Cl are as follows: Figure 3 As shown, the horizontal axis 2 Theta represents the diffraction angle (degree), and the vertical axis Intensity represents the intensity. The results show that TAPT exhibits better crystallization after reacting with hydrogen chloride inorganic acid. Figure 4 and Figure 5 The figures show charge-discharge curves for different cycle numbers and coulombic efficiency tests during cycling. The results indicate that the zinc-iodine full cell exhibits higher stability during cycling, suggesting that the non-metallic organic framework material TAPT.Cl has a more stable iodine loading.

[0044] Example 2 This embodiment provides a porous non-metallic organic framework material TT.Br, and applies the porous non-metallic organic framework material TT.Br to an aqueous zinc-iodine battery, as detailed below: 100 mg of organic amine (TT) was dissolved in 20 mL of tetrahydrofuran (THF) to prepare a 5 mg / mL solution. An excess of 48 wt% inorganic acid HBr aqueous solution was slowly added dropwise. The mixture was stirred at room temperature for 1 h, centrifuged, washed with an appropriate amount of THF, and dried in a vacuum drying oven at 60 °C for 12 h. The resulting sample (porous non-metallic organic framework material TT.Br) was removed from the drying oven and stored in a desiccator for later use.

[0045] A porous non-metallic organic framework material TT.Br, prepared by neutralization of organic amines and inorganic acids, was mixed with Ketjen black and PVDF in a mass ratio of 6:3:1 using NMP as a solvent. The mixture was then uniformly coated onto a 12 mm diameter hydrophilic carbon cloth current collector. The current collector was then dried in a vacuum oven at 60 °C for 12 h. The electrode was then immersed in a 1.0 M ZnI₂ solution for 30 min and dried in a vacuum oven at 40 °C for 12 h, completing the preparation of the iodine-loaded host electrode. The active iodine loading was approximately 6 mg. Using this iodine-loaded positive electrode as the positive electrode, a 1 M ZnSO₄ aqueous solution as the electrolyte, zinc foil as the negative electrode, and a glass fiber membrane as the separator, an aqueous zinc-iodine energy storage battery was assembled.

[0046] The aqueous zinc-iodine battery underwent chemical performance testing, and its performance at 1.0 A·g -1 It can release ~140 mAh·g -1 It has reversible capacity. And after 8000 cycles, the capacity retention rate is 74%.

[0047] Example 3 This embodiment provides a porous non-metallic organic framework material TTBT.Cl, and applies the porous non-metallic organic framework material TTBT.Cl to an aqueous zinc-iodine battery, as detailed below: 100 mg of organic amine (TTBT) was dissolved in 20 mL of tetrahydrofuran (THF) to prepare a 5 mg / mL solution. A 1.25 M inorganic acid HCl methanol solution was slowly added dropwise. The mixture was stirred at room temperature for 1 h, centrifuged, washed with an appropriate amount of THF, and dried in a vacuum drying oven at 60 °C for 12 h. The resulting sample (porous non-metallic organic framework material TTBT.Cl) was removed from the drying oven and stored in a desiccator for later use.

[0048] A porous non-metallic organic framework material TTBT.Cl, prepared by neutralization of organic amines and inorganic acids, was mixed with Ketjen black and PVDF in a mass ratio of 7:2:1 using NMP as a solvent. The mixture was then uniformly coated onto a 12 mm diameter hydrophilic carbon cloth current collector. The current collector was then dried in a vacuum oven at 60 °C for 12 h. The electrode was then immersed in a 1.0 M ZnI₂ solution for 30 min and dried in a vacuum oven at 40 °C for 12 h, completing the preparation of the iodine-loaded host electrode. The active iodine loading was approximately 4 mg. Using this iodine-loaded positive electrode as the positive electrode, a 1 M ZnSO₄ aqueous solution as the electrolyte, zinc foil as the negative electrode, and a glass fiber membrane as the separator, an aqueous zinc-iodine battery was assembled.

[0049] The aqueous zinc-iodine battery underwent chemical performance testing, and its performance at 1.0 A·g -1 It can release ~160 mAh·g -1It has reversible capacity. And after 7500 cycles, the capacity retention rate is 82%.

[0050] In summary, this invention provides a porous non-metallic organic framework material and its preparation method, as well as an aqueous zinc-iodine battery. The preparation method of the porous non-metallic organic framework material includes the following steps: mixing an organic amine with an organic solvent to obtain an organic amine solution; mixing the organic amine solution with an inorganic acid solution and stirring to obtain a porous non-metallic organic framework material (N-MOFs). This invention forms a porous organic ammonium halide framework material by combining organic amine cations with inorganic acid anions to form metal-free, tightly packed ion clusters. Based on the high porosity and large specific surface area of ​​the non-metallic organic framework material, the iodine loading capacity of the host cell can be improved. Due to the interaction between the nitrogen-containing active sites of the porous non-metallic organic framework material and iodine, the polyiodide ion shuttle diffusion effect can be effectively suppressed, improving the iodine interconversion rate while accelerating the iodine reaction kinetics. This significantly improves the coulombic efficiency and cycle stability of the zinc-iodine energy storage battery and suppresses its self-discharge, reducing specific capacity decay.

[0051] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A method for preparing a porous non-metallic organic framework material, characterized in that, The method comprises the steps of: mixing an organic amine with an organic solvent to obtain an organic amine solution; mixing the organic amine solution with an inorganic acid solution, and stirring to obtain a porous non-metallic organic framework material.

2. The method for preparing porous non-metallic organic framework materials according to claim 1, characterized in that, The organic amine is selected from one or more of 1,3,5-tris(4-aminophenyl)benzene, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine, and 4',4''',4'''''-(1,3,5-triazine-2,4,6-triyl)tris(([1,1'-biphenyl]-4-amine)).

3. The method for preparing porous non-metallic organic framework materials according to claim 1, characterized in that, The concentration of the organic amine solution is greater than or equal to 5 mg / mL.

4. The method for preparing porous non-metallic organic framework materials according to claim 1, characterized in that, The organic solvent is selected from one or more of acetone, dichloromethane, hexafluoroisopropanol, methanol, ethyl acetate, chlorobenzene, 1,4-dioxane, methyltetrahydrofuran, and tetrahydrofuran.

5. The method for preparing porous non-metallic organic framework materials according to claim 1, characterized in that, The inorganic acid is one or more of hydrogen chloride methanol solution and hydrogen bromide aqueous solution.

6. A porous non-metallic organic framework material, characterized in that, The porous non-metallic organic framework material is prepared by the method of any one of claims 1-5.

7. The porous non-metallic organic framework material of claim 6, wherein, The porous non-metallic organic framework material is one of an amino halide salt of 1,3,5-tris(4-aminophenyl)benzene and chlorine, an amino halide salt of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine and bromine, and an amino halide salt of 4',4''',4'''''-(1,3,5-triazine-2,4,6-triyl)tris(([1,1'-biphenyl]-4-amine)) and chlorine.

8. An aqueous zinc-iodine battery, characterized by, The positive electrode sheet comprises a current collector, a positive electrode active layer arranged on the surface of the current collector, and iodine elements loaded on the positive electrode active layer; the positive electrode active layer contains the porous non-metallic organic framework material of any one of claims 6-7.

9. The aqueous zinc-iodine battery of claim 8, wherein, The positive electrode active layer further contains a conductive additive and a binder; the mass ratio of the porous non-metallic organic framework material, the conductive additive, and the binder is (6-7):(2-3):

1.

10. The aqueous zinc-iodine battery of claim 9, wherein, The conductive additive is selected from one or more of ketjen black, acetylene black, and carbon black; the binder is selected from one or more of polyvinylidene fluoride, polytetrafluoroethylene, and hydroxymethyl cellulose; and the current collector is selected from one of carbon cloth, carbon paper, titanium mesh, and titanium foil.

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