Flexible acylhydrazone-based hydrogen bond framework, polymer, preparation method, derivative porous carbon material and application thereof

Abstract

The invention discloses a flexible acylhydrazone-based hydrogen bond framework, a polymer, a preparation method of the flexible acylhydrazone-based hydrogen bond framework, a derivative porous carbon material of the flexible acylhydrazone-based hydrogen bond framework and the polymer and application of the derivative porous carbon material, and the novel crystalline acylhydrazone-based hydrogen bond framework and the polymer material are synthesized through a simple reflux method by utilizing the synergistic effect of flexible aliphatic chain dihydrazide and rigid aromatic dialdehyde or diketone. The material has abundant hydrogen bond donors and acceptors and various conformations, and is stable in state. The nitrogen-rich hierarchical-pore conductive porous carbon material is simple and convenient to operate and controllable in pore diameter, and does not need to be additionally added or only needs a very small amount of activating agent. The prepared porous carbon material shows high specific surface area and graphitization degree, and contains abundant micropore and mesoporous structures. The material is especially suitable for the positive electrode of an aqueous zinc-iodine battery, can significantly inhibit the shuttle effect of iodine in the use process of the battery, and shows high specific capacity and excellent cycle stability.

Description

Technical Field

[0001] This invention relates to the fields of supramolecular chemical functional materials and crystalline polymer carbonization technology, specifically to flexible acylhydrazone hydrogen bonding frameworks, polymers, preparation methods, and their derived porous carbon materials and applications. Background Technology

[0002] Hydrogen-bonded organic frameworks (HOFs) are a class of ordered porous crystalline materials assembled through intermolecular hydrogen bonds. They offer advantages such as mild synthesis conditions, ease of obtaining single crystals, and solubility and renewability. In constructing HOF structural units, rigid aromatic diacid hydrazides are widely used due to their strong conjugation and well-defined directionality, resulting in a regular and stable framework structure. However, flexible diacid hydrazides, especially those containing aliphatic chains, are often unfavorable for the formation of ordered crystalline structures due to their variable conformations and high degrees of freedom, leading to amorphous or polymeric products. Chinese Patent (Publication No.: CN117362674A) discloses a class of porous hydrogen-bonded framework materials (HOFs) based on acylhydrazone covalent macrocycles, synthesized in a one-pot solvothermal process using a meta-diacetyl aromatic compound and a rigid diacid hydrazide under conditions free of metal ions and acid catalysts. The resulting material possesses a highly ordered crystalline structure, forming a stable two-dimensional layered structure through intermolecular hydrogen bonding and π-π stacking, which further stacks to form a three-dimensional porous framework containing one-dimensional microporous channels. This approach primarily uses rigid diacid hydrazides as structural units to construct three-dimensional porous materials. Therefore, systematic research on the use of flexible diacid hydrazides in the construction of crystalline porous materials is currently lacking.

[0003] Acylhydrazone bonds are a typical type of dynamic covalent bond, exhibiting reversible formation and decomposition characteristics, and have attracted attention in self-healing materials and reconfigurable polymers. Linear or cross-linked acylhydrazone polymers can be formed using dihydrazides and diketones as units. These polymers can form ordered frameworks through linear polymers or via hydrogen bonding / π-π interactions. Introducing metal ions to participate in network formation can further enhance their ordered structure.

[0004] Aqueous zinc-iodine batteries are considered a promising alternative to lithium-ion batteries due to abundant raw material resources and the safety of aqueous solutions. However, they are currently limited by issues such as polyiodine anion shuttle in the iodine cathode, dendrite growth in the zinc anode, and low mass transfer efficiency, and remain in the theoretical guidance stage, not yet achieving large-scale production. Recent research indicates that the core solution to the iodine cathode problem lies in developing highly conductive and highly porosity iodine host materials, as well as surface / structure modulation to enhance iodine adsorption and reversible reaction. Porous carbon materials, due to their designable structure, have emerged as one solution. As an iodine carrier, porous carbon provides electron conduction pathways and abundant pores for iodine adsorption and fixation. Loading iodine into heteroatom-doped hierarchical porous carbon can simultaneously achieve physical confinement and chemical fixation of iodine, and provide ion transport channels, thereby mitigating self-discharge and capacity decay caused by polyiodine anion shuttle and significantly improving battery cycle stability. Therefore, how to control the performance of porous carbon through structural design is a crucial factor affecting the performance of aqueous zinc-iodine batteries. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention aims to provide a flexible acylhydrazone hydrogen-bonded framework, polymer, preparation method, and derived porous carbon materials and applications.

[0006] To achieve the above objectives, the first aspect of the present invention provides:

[0007] A flexible acylhydrazone hydrogen bonding framework, the structural formula of which is shown in any of the following examples:

[0008]

[0009]

[0010] The second aspect of the present invention provides:

[0011] A method for preparing a flexible acylhydrazone hydrogen-bonded framework includes the following steps:

[0012] The dihydrazide starting material is dissolved in a solvent, heated, and then a diacetyl starting material is added. A catalyst may or may not be added as needed. The reaction is carried out under reflux at a constant temperature to obtain the corresponding product. An example reaction is shown below:

[0013]

[0014] Preferably, as one of the methods for preparing a flexible acylhydrazone hydrogen-bonded framework, equivalent amounts of carbazone, oxaloyl dihydrazide, malonyl dihydrazide, succinyl dihydrazide, glutaryl dihydrazide, adipic acid dihydrazide, dodecyl dihydrazide, terephthalic acid dihydrazide, 4,4'-biphenyl dicarboxylic acid dihydrazide, 2,6-naphthalenedicarboxylic acid dihydrazide, thiodi(acetylhydrazide), 2,5-thiophenediacid dihydrazide, octafluoroadipate dihydrazide, trans, trans-2,4-hexadienediacid dihydrazide, 1,2-ethylidene di(carbamoyl hydrazide), 1,2-ethylidene bis(hydrazine), 1,3 One of 1,4-propylidene bis(hydrazine) and 1,4-butylidene bis(hydrazine) is dissolved in one or more of dimethyl sulfoxide, N,N'-dimethylformamide, methanol, acetic acid, N-methylpyrrolidone, and dichloromethane. The mixture is heated to 120°C, and then an equivalent amount of 2,6-diacetylpyridine is added. One of nickel sulfate, nickel chloride, nickel perchlorate, nickel nitrate, nickel acetate, copper sulfate, copper chloride, copper perchlorate, copper nitrate, and copper acetate is added with little or no addition. The mixture is refluxed to give the corresponding acylhydrazone HOF product.

[0015] Preferably, as another method for preparing a flexible acylhydrazone hydrogen-bonded framework, equivalent amounts of carbazone, oxaloyl dihydrazide, malonyl dihydrazide, succinyl dihydrazide, glutaryl dihydrazide, adipic dihydrazide, dodecyl dihydrazide, terephthalic dihydrazide, 4,4'-biphenyldicarboxylic acid dihydrazide, 2,6-naphthalenedicarboxylic acid dihydrazide, thiodi(acetylhydrazide), 2,5-thiophenediacid dihydrazide, octafluoroadipate dihydrazide, trans, trans-2,4-hexadiene dichydrazide, 1,2-ethylidene di(carbamoyl hydrazide), 1,2-ethylidene bis(hydrazine), 1,3-propylene dihydrazide One of hydrazinobis(hydrazinobis) and 1,4-butylenebis(hydrazinobis) is dissolved in one or more of dimethyl sulfoxide, N,N'-dimethylformamide, methanol, acetic acid, N-methylpyrrolidone, and dichloromethane. The mixture is heated to 120°C, and then an equivalent amount of 2,6-dimethyl-3,5-diacetylpyridine is added. One of nickel sulfate, nickel chloride, nickel perchlorate, nickel nitrate, nickel acetate, copper sulfate, copper chloride, copper perchlorate, copper nitrate, and copper acetate is added with little or no addition. The mixture is refluxed to give the corresponding acylhydrazone HOF product.

[0016] Preferably, as another method for preparing a flexible acylhydrazone hydrogen-bonded framework, equivalent amounts of carbazone, oxaloyl dihydrazide, malonyl dihydrazide, succinyl dihydrazide, glutaryl dihydrazide, adipic dihydrazide, dodecyl dihydrazide, terephthalic dihydrazide, 4,4'-biphenyldicarboxylic acid dihydrazide, 2,6-naphthalenedicarboxylic acid dihydrazide, thiodi(acetylhydrazide), 2,5-thiophenediacid dihydrazide, octafluoroadipate dihydrazide, trans, trans-2,4-hexadienediacid dihydrazide, 1,2-ethylidene di(carbamoyl hydrazide), 1,2-ethylidene bis(hydrazine), 1,3-propylidene One of bis(hydrazine) and 1,4-butylenebis(hydrazine) is dissolved in one or more of dimethyl sulfoxide, N,N'-dimethylformamide, methanol, acetic acid, N-methylpyrrolidone, and dichloromethane. The mixture is heated to 120°C, and then an equivalent amount of 2,4,6-trimethyl-3,5-diacetylpyridine is added. One of nickel sulfate, nickel chloride, nickel perchlorate, nickel nitrate, nickel acetate, copper sulfate, copper chloride, copper perchlorate, copper nitrate, and copper acetate is added with little or no addition. The mixture is refluxed to give the corresponding acylhydrazone HOF product.

[0017] Preferably, as another method for preparing a flexible acylhydrazone hydrogen-bonded framework, equivalent amounts of carbazone, oxaloyl dihydrazide, malonyl dihydrazide, succinyl dihydrazide, glutaryl dihydrazide, adipic dihydrazide, dodecyl dihydrazide, terephthalic dihydrazide, 4,4'-biphenyl dicarboxylic acid dihydrazide, 2,6-naphthalenedicarboxylic acid dihydrazide, thiodi(acetylhydrazide), 2,5-thiophenediacid dihydrazide, octafluoroadipate dihydrazide, trans, trans-2,4-hexadienediacid dihydrazide, 1,2-ethylidene di(carbamoyl hydrazide), 1,2-ethylidene bis(hydrazine), 1, One of 3-propylidene bis(hydrazine) and 1,4-butylidene bis(hydrazine) is dissolved in one or more of dimethyl sulfoxide, N,N'-dimethylformamide, methanol, acetic acid, N-methylpyrrolidone, and dichloromethane. The mixture is heated to 120°C, and then an equivalent amount of N,9-diacetylguanine is added. One of nickel sulfate, nickel chloride, nickel perchlorate, nickel nitrate, nickel acetate, copper sulfate, copper chloride, copper perchlorate, copper nitrate, and copper acetate is added with little or no addition. The mixture is refluxed to give the corresponding acylhydrazone HOF product.

[0018] The third aspect of the present invention is provided as follows:

[0019] A flexible acylhydrazone-based polymer material, wherein the structural formula of the flexible acylhydrazone-based polymer material is any one of the following

[0020] As shown:

[0021]

[0022]

[0023] The degree of polymerization n is 10 to 30.

[0024] Preferably, by controlling the degree of polymerization to be between 10 and 30, it is ensured that the polymer material has sufficient molecular weight to form a stable crystalline or porous structure, while not being too large to reduce its flexibility and processability. This allows the rigid aromatic units in the material to form a stable crystalline or porous framework structure, ensuring the stability of the overall architecture. Simultaneously, the flexible aliphatic dihydrazide, acting as a connecting unit, endows the material with a certain degree of dynamism and conformational freedom. This not only helps alleviate internal molecular stress but also promotes intermolecular interactions, enhancing the overall performance and application potential of the material. Furthermore, controlling the degree of polymerization between 10 and 30 also ensures that the material can be effectively transformed into a porous carbon material with high specific surface area, abundant pore structure, and excellent electrical conductivity during subsequent carbonization.

[0025] The fourth aspect of the present invention is provided as follows:

[0026] A method for preparing a flexible acylhydrazone-based polymer material includes the following steps:

[0027] The dihydrazide raw material is dissolved in a solvent, heated, and then a dialdehyde raw material is added. A catalyst may be added selectively or not, depending on the need. The reaction is carried out under reflux at a constant temperature to obtain the corresponding product. An exemplary reaction formula is as follows:

[0028]

[0029] Preferably, as a method for preparing one type of flexible acylhydrazone polymer material, an equivalent amount of one of the following: carbazone, oxaloyl dihydrazide, malonyl hydrazide, succinyl hydrazide, adipyl hydrazide, dodecyl dihydrazide, terephthalic acid dihydrazide, and 4,4'-biphenyl dicarboxylic acid dihydrazide is dissolved in one or more of dimethyl sulfoxide, N,N'-dimethylformamide, methanol, acetic acid, N-methylpyrrolidone, and dichloromethane, heated to 120°C, and then an equivalent amount of glyoxal is added. One of the following is added in small amounts or not at all: nickel sulfate, nickel chloride, nickel perchlorate, nickel nitrate, nickel acetate, copper sulfate, copper chloride, copper perchlorate, copper nitrate, and copper acetate. The mixture is then refluxed to obtain the corresponding acylhydrazone polymer product.

[0030] Preferably, as another method for preparing a flexible acylhydrazone polymer material, an equivalent amount of one of the following: carbazide, oxaloyl hydrazine, malonyl hydrazine, succinyl hydrazine, adipyl hydrazine, dodecyl dihydrazine, terephthalic hydrazine, and 4,4'-biphenyl dicarboxylic acid dihydrazine is dissolved in one or more of dimethyl sulfoxide, N,N'-dimethylformamide, methanol, acetic acid, N-methylpyrrolidone, and dichloromethane, heated to 120°C, and then an equivalent amount of glutaraldehyde is added. No or a small amount of one of the following: nickel sulfate, nickel chloride, nickel perchlorate, nickel nitrate, nickel acetate, copper sulfate, copper chloride, copper perchlorate, copper nitrate, and copper acetate are added, and the mixture is refluxed to obtain the corresponding acylhydrazone polymer product.

[0031] Preferably, as another method for preparing a flexible acylhydrazone polymer material, an equivalent amount of one of the following: carbazide, oxaloyl dihydrazide, malonyl hydrazide, succinyl hydrazide, adipyl hydrazide, dodecyl dihydrazide, terephthalic acid dihydrazide, and 4,4'-biphenyl dicarboxylic acid dihydrazide is dissolved in one or more of dimethyl sulfoxide, N,N'-dimethylformamide, methanol, acetic acid, N-methylpyrrolidone, and dichloromethane, heated to 120°C, and then an equivalent amount of terephthalaldehyde is added, with no or a small amount of one of the following: nickel sulfate, nickel chloride, nickel perchlorate, nickel nitrate, nickel acetate, copper sulfate, copper chloride, copper perchlorate, copper nitrate, and copper acetate added, and the mixture is refluxed to obtain the corresponding acylhydrazone polymer product.

[0032] The fifth aspect of the present invention provides:

[0033] A porous carbon material is prepared from the aforementioned flexible acylhydrazone hydrogen bonding framework or the aforementioned flexible acylhydrazone polymer material as raw materials.

[0034] Specifically, the flexible acylhydrazone hydrogen-bonded framework or the flexible acylhydrazone polymer material is placed in a ceramic boat, and a pore-forming agent is selectively added or not added. The pore-forming agent is one or more of potassium hydroxide, potassium carbonate, potassium bicarbonate, calcium carbonate, sodium hydroxide, sodium carbonate, and sodium bicarbonate, and the addition amount is 5% to 20%. Subsequently, it is carbonized at high temperature in a tube furnace under an inert gas atmosphere. The carbonization temperature is 700 to 900°C, the heating rate is 3 to 10°C / min, and the carbonization time is 1 to 5 hours to obtain the corresponding porous carbon material product.

[0035] To address the shortcomings of existing porous carbon materials, such as uncontrollable pore size, complex preparation process, and the need for additional activators, this application provides a method for preparing porous carbon materials using acylhydrazone hydrogen bonding frameworks and polymer materials as precursors. The method is simple to operate, the pore size is controllable, and the corresponding porous carbon materials can be obtained without the need for additional activators or with only a very small amount of activators.

[0036] The sixth aspect of the present invention provides:

[0037] Application of a porous carbon material in the preparation of aqueous zinc-iodine batteries.

[0038] Specifically, the porous carbon material is used to prepare a positive electrode for use in aqueous zinc-iodine batteries.

[0039] The beneficial effects of this invention are as follows:

[0040] 1. Building upon the previous patent (CN202311429200.4), this application innovatively employs flexible aliphatic chain dihydrazides as structural units, synergistically interacting with rigid aromatic dialdehydes or diketones to construct novel crystalline acylhydrazone hydrogen-bonded frameworks and polymer materials. Simultaneously, a method for preparing nitrogen-rich hierarchical porous conductive carbon materials through carbonization conversion is developed for the first time, thereby deriving these materials into porous carbon materials and enhancing their application potential in the field of aqueous zinc-iodine batteries.

[0041] 2. This application uses m-diacetylpyridine ring and its derivatives, m-diacetylpurine ring, m-diacetylbenzene ring and rigid or flexible dihydrazides as raw materials to synthesize a class of acylhydrazone hydrogen-bonded organic framework materials by reflux method without the action of catalyst and inexpensive solvent. It has the advantages of convenient operation, no need for complicated purification steps and high yield.

[0042] 3. This application uses flexible dialdehyde or rigid p-dialdehyde compounds and rigid or flexible dihydrazides as raw materials to synthesize a class of acylhydrazone polymers by reflux method without the action of catalysts and inexpensive solvents. It has the advantages of convenient operation, no need for complicated purification steps and high yield.

[0043] 4. The acylhydrazone hydrogen bond framework and polymer materials synthesized in this application have abundant hydrogen bond donors and acceptors and diverse conformations, and are stable in state.

[0044] 5. This application also uses the above-mentioned acylhydrazone hydrogen bonding framework and polymer materials as precursors to synthesize derived porous carbon materials, which have the advantages of simple operation process, controllable pore size, and no need to add or only a very small amount of activator.

[0045] 6. The porous carbon material prepared in this application has a hierarchical pore structure with abundant micropores and mesopores, high specific surface area, and high degree of graphitization.

[0046] 7. The porous carbon material prepared in this application can be used as the positive electrode of an aqueous zinc-iodine battery. During battery use, it can significantly suppress the shuttle effect of iodine and has high specific capacity and excellent cycle stability.

[0047] 8. This application preliminarily studies the key influencing factors of pore size control, pore retention and heteroatom doping in the process of preparing porous carbon from porous crystalline materials. The research results provide important technical guidance and theoretical basis for the subsequent large-scale synthesis of high-performance porous carbon materials. Attached Figure Description

[0048] Figure 1 (a) is the X-ray powder diffraction pattern of mHOF-101 in Example 1 of the present invention; (b) is the infrared spectrum of mHOF-101.

[0049] Figure 2(a) is the X-ray powder diffraction pattern of HC-700-101 in Example 1 of the present invention; (b) is the X-ray powder diffraction pattern of HCC-700-101.

[0050] Figure 3 (a) is the X-ray powder diffraction pattern of HC-800-101 in Example 1 of the present invention; (b) is the X-ray powder diffraction pattern of HCC-800-101.

[0051] Figure 4 (a) is the X-ray powder diffraction pattern of HC-900-101 in Example 1 of the present invention; (b) is the X-ray powder diffraction pattern of HCC-900-101.

[0052] Figure 5 (a) is the X-ray powder diffraction pattern of mHOF-206 in Example 2 of the present invention; (b) is the infrared spectrum of mHOF-206.

[0053] Figure 6 (a) is the X-ray powder diffraction pattern of mHOF-102 in Example 3 of the present invention; (b) is the infrared spectrum of mHOF-102.

[0054] Figure 7 (a) is the X-ray powder diffraction pattern of mHOF-103 in Example 4 of the present invention; (b) is the infrared spectrum of mHOF-103.

[0055] Figure 8 (a) is the X-ray powder diffraction pattern of mHOF-106 in Example 5 of the present invention; (b) is the infrared spectrum of mHOF-106.

[0056] Figure 9 (a) is the X-ray powder diffraction pattern of Poly-307 in Example 6 of the present invention; (b) is the infrared spectrum of Poly-307.

[0057] Figure 10 (a) is the X-ray powder diffraction pattern of Poly-305 in Example 7 of the present invention; (b) is the infrared spectrum of Poly-305.

[0058] Figure 11 (a) is the X-ray powder diffraction pattern of Poly-107 in Example 8 of the present invention; (b) is the infrared spectrum of Poly-107.

[0059] Figure 12 (a) is the X-ray powder diffraction pattern of Poly-207 in Example 9 of the present invention; (b) is the infrared spectrum of Poly-207.

[0060] Figure 13(a) is a long-cycle battery performance diagram of HC-900-101 in Example 10 of the present invention; (b) is a long-cycle battery performance diagram of HCC-900-101.

[0061] Figure 14 The pore distribution and corresponding pore area of ​​HC-700-101, HC-800-101, HC-900-101 and HCC-900-101 are shown.

[0062] Figure 15 The XPS full spectrum for HC-700-101, HC-800-101 and HC-900-101. Detailed Implementation

[0063] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art should understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased on the market.

[0064] This invention application, based on a previous patent (CN202311429200.4), innovatively introduces flexible aliphatic chain dihydrazides as structural units, which synergistically interact with rigid aromatic dialdehydes or diketones to construct novel crystalline acylhydrazone hydrogen-bonding frameworks and polymer materials. Simultaneously, it develops for the first time a method for preparing nitrogen-rich hierarchical porous conductive carbon materials through carbonization conversion. It provides flexible acylhydrazone hydrogen-bonding frameworks, polymers, preparation methods, and the application of derived porous carbon materials in batteries. Raw materials include dihydrazide compounds such as carbamate, oxaloyl hydrazide, malonyl hydrazide, succinic hydrazide, glutaryl hydrazide, adipyl hydrazide, dodecyl dihydrazide, terephthalic hydrazide, 4,4'-biphenyldicarboxylic acid dihydrazide, 2,6-naphthalenedicarboxylic acid hydrazide, thiodi(acetylhydrazide), 2,5-thiophenediacid dihydrazide, octafluoroadipate dihydrazide, trans, trans-2,4-hexadiene diazide, and 1,2-ethylhexene. Di(carbamoylhydrazine), 1,2-ethylidene bis(hydrazine), 1,3-propylidene bis(hydrazine), 1,4-butylidene bis(hydrazine); diacetyl compounds 2,6-diacetylpyridine, 2,6-dimethyl-3,5-diacetylpyridine, 2,4,6-trimethyl-3,5-diacetylpyridine, N,9-diacetylguanine, 1,3-diacetylbenzene and dialdehyde compounds isophthalaldehyde, 2,6-pyridinedialdehyde, glyoxal, glutaraldehyde, terephthalaldehyde. The embodiments involve the separate reactions of dialdehyde / diacetyl compounds with diacylhydrazine compounds. Therefore, the reactants involved in the various embodiments of this application described below do not conflict with each other and can be combined with each other, all falling within the scope of protection of this application.

[0065] Example 1

[0066] The preparation method of mHOF-101 and its derived porous carbon includes the following steps:

[0067] First, 194.2 mg of terephthalic hydrazide was dissolved in 10 mL of dimethyl sulfoxide and heated to 120 °C. Then, 163.2 mg of 2,6-diacetylpyridine was added, and the mixture was refluxed for 12 h while maintaining the temperature. After the reaction was completed, a pale yellow precipitate was formed. After filtration, the precipitate was washed with 3 × 10 mL of methanol and dried in an oven at 120 °C for 3 h to obtain a pale yellow powder, named mHOF-101. 1 g of mHOF-101 powder was placed in a porcelain boat and carbonized in a tube furnace at 700 °C, 800 °C, and 900 °C for 3 h at a heating rate of 5 °C / min under a nitrogen atmosphere of 0.5 L / min. The black solid powders were collected and named HC-700-101, HC-800-101, and HC-900-101, respectively. 1 g of mHOF-101 powder and 0.05 g of calcium carbonate were placed in a mortar and ground thoroughly for 30 min. The mixed powder was then placed in a porcelain boat and carbonized in a tube furnace at 700℃, 800℃, and 900℃ for 3 h at a heating rate of 5℃ / min under a nitrogen atmosphere of 0.5 L / min. The black solid powder was collected, and 30 mL of 0.1 M dilute hydrochloric acid was added and stirred for 30 min. The mixture was filtered, washed with distilled water until the filtrate was neutral, and dried in an oven at 120℃ for 3 h to obtain the black solid powder, which was named HCC-700-101, HCC-800-101, and HCC-900-101, respectively. By controlling the inherent pore size of the material itself and changing the temperature and the amount of activator added, pore size control and pore retention were achieved. At the same time, due to the abundant nitrogen content of the hydrazide group, the obtained porous carbon has considerable nitrogen atom doping.

[0068] Figure 1 (a) is the X-ray powder diffraction pattern of mHOF-101. Figure 1 (b) is the infrared spectrum of mHOF-101. Figure 2 (a) is the X-ray powder diffraction pattern of HC-700-101. Figure 2 (b) is the X-ray powder diffraction pattern of HCC-700-101. Figure 3 (a) is the X-ray powder diffraction pattern of HC-800-101. Figure 3 (b) is the X-ray powder diffraction pattern of HCC-800-101. Figure 4 (a) is the X-ray powder diffraction pattern of HC-900-101. Figure 4 (b) is the X-ray powder diffraction pattern of HCC-900-101.

[0069] from Figure 1(a) As can be seen, the X-ray powder diffraction pattern shows that mHOF-101 has obvious diffraction peaks, indicating that the material is highly crystalline with a well-defined crystalline structure, which provides a good precursor basis for subsequent carbonization. Figure 2 (a)- Figure 4 (b) It can be seen that as the carbonization temperature increases, the material gradually changes from an ordered crystalline state to a partially amorphous or porous carbon material containing graphite microcrystals.

[0070] Example 2

[0071] The preparation method of mHOF-206 and its derived porous carbon includes the following steps:

[0072] First, 174.2 mg of adipic hydrazide was dissolved in 10 mL of dimethyl sulfoxide and heated to 120 °C. Then, 163.2 mg of 2,6-diacetylpyridine was added, and the mixture was refluxed for 12 h while maintaining the temperature constant. After the reaction was completed, a pale yellow precipitate was formed. After filtration, the precipitate was washed with 3 × 10 mL of methanol and dried in an oven at 120 °C for 3 h to obtain a pale yellow powder, named mHOF-206. 1 g of mHOF-206 powder was placed in a porcelain boat and carbonized in a tube furnace at 700 °C, 800 °C, and 900 °C for 3 h at a heating rate of 5 °C / min under a nitrogen atmosphere of 0.5 L / min. The black solid powders were collected and named HC-700-206, HC-800-206, and HC-900-206, respectively. 1 g of mHOF-206 powder and 0.05 g of calcium carbonate were placed in a mortar and ground thoroughly for 30 min. The mixed powder was then placed in a porcelain boat and carbonized in a tube furnace at 700℃, 800℃, and 900℃ for 3 h at a heating rate of 5℃ / min under a nitrogen atmosphere of 0.5 L / min. The black solid powder was collected, and 30 mL of 0.1 M dilute hydrochloric acid was added and stirred for 30 min. The mixture was filtered, washed with distilled water until the filtrate was neutral, and dried in an oven at 120℃ for 3 h to obtain the black solid powder, which was named HCC-700-206, HCC-800-206, and HCC-900-206, respectively. By controlling the inherent pore size of the material itself and changing the temperature and the amount of activator added, pore size control and pore retention were achieved. At the same time, due to the abundant nitrogen content of the hydrazide group, the obtained porous carbon has considerable nitrogen atom doping.

[0073] Figure 5 (a) is the X-ray powder diffraction pattern of mHOF-206. Figure 5 (b) is the infrared spectrum of mHOF-206.

[0074] from Figure 5 (a) Figure 5(b) It can be seen that mHOF-206 has a well-defined crystalline structure and specific acylhydrazone functional groups, which provide a good precursor basis for subsequent carbonization. As the carbonization temperature increases, the material gradually transforms from an ordered crystalline state to a partially amorphous or porous carbon material containing graphite microcrystals.

[0075] Example 3

[0076] The preparation method of mHOF-102 and its derived porous carbon includes the following steps:

[0077] First, 194.2 mg of terephthalic hydrazide was dissolved in 10 mL of dimethyl sulfoxide and heated to 120 °C. Then, 191.3 mg of 2,6-dimethyl-3,5-diacetylpyridine was added, and the mixture was refluxed for 12 h while maintaining the temperature constant. After the reaction was completed, a yellow precipitate was formed. After filtration, the precipitate was washed with 3 × 10 mL of methanol and dried in an oven at 120 °C for 3 h to obtain a yellow powder, named mHOF-102. 1 g of mHOF-102 powder was placed in a porcelain boat and carbonized in a tube furnace at 700 °C, 800 °C, and 900 °C for 3 h at a heating rate of 5 °C / min under a nitrogen atmosphere of 0.5 L / min. The black solid powders were collected and named HC-700-102, HC-800-102, and HC-900-102, respectively. 1 g of mHOF-102 powder and 0.05 g of calcium carbonate were placed in a mortar and ground thoroughly for 30 min. The mixed powder was then placed in a porcelain boat and carbonized in a tube furnace at 700℃, 800℃, and 900℃ for 3 h at a heating rate of 5℃ / min under a nitrogen atmosphere of 0.5 L / min. The black solid powder was collected, and 30 mL of 0.1 M dilute hydrochloric acid was added and stirred for 30 min. The mixture was filtered, washed with distilled water until the filtrate was neutral, and dried in an oven at 120℃ for 3 h to obtain the black solid powder, which was named HCC-700-102, HCC-800-102, and HCC-900-102, respectively. By controlling the inherent pore size of the material itself and changing the temperature and the amount of activator added, pore size control and pore retention were achieved. At the same time, due to the abundant nitrogen content of the hydrazide group, the obtained porous carbon has considerable nitrogen atom doping.

[0078] Figure 6 (a) is the X-ray powder diffraction pattern of mHOF-102. Figure 6 (b) is the infrared spectrum of mHOF-102.

[0079] from Figure 6 (a) Figure 6(b) It can be seen that mHOF-102 has a well-defined crystalline structure and specific acylhydrazone functional groups, which provide a good precursor basis for subsequent carbonization. As the carbonization temperature increases, the material gradually transforms from an ordered crystalline state to a partially amorphous or porous carbon material containing graphite microcrystals.

[0080] Example 4

[0081] The preparation method of mHOF-103 and its derived porous carbon includes the following steps:

[0082] First, 194.2 mg of terephthalic hydrazide was dissolved in 10 mL of dimethyl sulfoxide and heated to 120 °C. Then, 203.3 mg of 2,4,6-trimethyl-3,5-diacetylpyridine was added, and the mixture was refluxed for 12 h while maintaining the temperature constant. After the reaction was completed, a brown precipitate was formed. After filtration, the precipitate was washed with 3 × 10 mL of methanol and dried in an oven at 120 °C for 3 h to obtain a brown powder, named mHOF-103. 1 g of mHOF-103 powder was placed in a porcelain boat and carbonized in a tube furnace at 700 °C, 800 °C, and 900 °C for 3 h at a heating rate of 5 °C / min under a nitrogen atmosphere of 0.5 L / min. The black solid powders were collected and named HC-700-103, HC-800-103, and HC-900-103, respectively. 1 g of mHOF-103 powder and 0.05 g of calcium carbonate were placed in a mortar and ground thoroughly for 30 min. The mixed powder was then placed in a porcelain boat and carbonized in a tube furnace at 700℃, 800℃, and 900℃ for 3 h at a heating rate of 5℃ / min under a nitrogen atmosphere of 0.5 L / min. The black solid powder was collected, and 30 mL of 0.1 M dilute hydrochloric acid was added and stirred for 30 min. The mixture was filtered, washed with distilled water until the filtrate was neutral, and dried in an oven at 120℃ for 3 h to obtain black solid powder, which was named HCC-700-103, HCC-800-103, and HCC-900-103, respectively. By controlling the inherent pore size of the material itself and changing the temperature and the amount of activator added, pore size control and pore retention were achieved. At the same time, due to the rich nitrogen content of the hydrazide group, the obtained porous carbon has considerable nitrogen atom doping.

[0083] Figure 7 (a) is the X-ray powder diffraction pattern of mHOF-103. Figure 7 (b) is the infrared spectrum of mHOF-103.

[0084] from Figure 7 (a) Figure 7(b) It can be seen that mHOF-103 has a well-defined crystalline structure and specific acylhydrazone functional groups, which provide a good precursor basis for subsequent carbonization. As the carbonization temperature increases, the material gradually transforms from an ordered crystalline state to a partially amorphous or porous carbon material containing graphite microcrystals.

[0085] Example 5

[0086] The preparation method of mHOF-106 and its derived porous carbon includes the following steps:

[0087] First, 194.2 mg of terephthalic hydrazide was dissolved in 10 mL of dimethyl sulfoxide and heated to 120 °C. Then, 235.2 mg of N,9-diacetylguanine was added, and the mixture was refluxed for 12 h while maintaining the temperature constant. After the reaction was completed, a gray precipitate was formed. After filtration, the precipitate was washed with 3 × 10 mL of methanol and dried in an oven at 120 °C for 3 h to obtain a gray powder, named mHOF-106. 1 g of mHOF-106 powder was placed in a porcelain boat and carbonized in a tube furnace at 700 °C, 800 °C, and 900 °C for 3 h at a heating rate of 5 °C / min under a nitrogen atmosphere of 0.5 L / min. The black solid powders were collected and named HC-700-106, HC-800-106, and HC-900-106, respectively. Take 1g of mHOF-106 powder and 0.05g of calcium carbonate and place them in a mortar. Grind them thoroughly for 30min. Place the mixed powder in a porcelain boat and carbonize it in a tube furnace at 700℃, 800℃ and 900℃ for 3h at a heating rate of 5℃ / min under a nitrogen atmosphere of 0.5L / min. Collect the black solid powder, add 30mL of 0.1M dilute hydrochloric acid and stir for 30min. Filter and wash with distilled water until the filtrate is neutral. Dry in an oven at 120℃ for 3h to obtain black solid powder, which are named HCC-700-106, HCC-800-106 and HCC-900-106, respectively.

[0088] Figure 8 (a) is the X-ray powder diffraction pattern of mHOF-106. Figure 8 (b) is the infrared spectrum of mHOF-106.

[0089] from Figure 8 (a) Figure 8 (b) It can be seen that mHOF-106 has a well-defined crystalline structure and specific acylhydrazone functional groups, which provide a good precursor basis for subsequent carbonization. With the increase of carbonization temperature, the material gradually transforms from an ordered crystalline state to a partially amorphous or porous carbon material containing graphite microcrystals. By controlling the inherent pore size of the material itself, changing the temperature and the amount of activator added, pore size regulation and pore retention are achieved; at the same time, due to the rich nitrogen content of the acylhydrazone groups, the resulting porous carbon has considerable nitrogen atom doping.

[0090] Example 6

[0091] The preparation method of Poly-307 and its derived porous carbon includes the following steps:

[0092] First, 194.2 mg of terephthalic acid hydrazide was dissolved in 10 mL of dimethyl sulfoxide and heated to 120 °C. Then, 134.1 mg of terephthalaldehyde was added, and the mixture was refluxed for 12 h while maintaining the temperature. After the reaction was complete, a white precipitate was formed. After filtration, the precipitate was washed with 3 × 10 mL of methanol and dried in an oven at 120 °C for 3 h to obtain a white powder, named Poly-307. Alternatively, 194.2 mg of terephthalic acid hydrazide was dissolved in 10 mL of dimethyl sulfoxide and heated to 120 °C. Then, 134.1 mg of terephthalaldehyde and 88.4 mg of nickel acetate were added, and the mixture was refluxed for 12 h while maintaining the temperature. After the reaction was complete, a white precipitate was formed. After filtration, the precipitate was washed with 3 × 10 mL of methanol and dried in an oven at 120 °C for 3 h to obtain a white powder, named Poly-307-Ni. Take 1g of Poly-307 powder and place it in a porcelain boat. Under a nitrogen atmosphere of 0.5L / min, carbonize it in a tube furnace at 700℃, 800℃ and 900℃ for 3h at a heating rate of 5℃ / min. Collect the black solid powder and name it PC-700-307, PC-800-307 and PC-900-307, respectively. 1 g of Poly-307 powder and 0.05 g of calcium carbonate were placed in a mortar and ground thoroughly for 30 min. The mixed powder was then placed in a porcelain boat and carbonized in a tube furnace at 700℃, 800℃, and 900℃ for 3 h at a heating rate of 5℃ / min under a nitrogen atmosphere of 0.5 L / min. The black solid powder was collected, and 30 mL of 0.1 M dilute hydrochloric acid was added and stirred for 30 min. The mixture was filtered, washed with distilled water until the filtrate was neutral, and dried in an oven at 120℃ for 3 h to obtain the black solid powder, which was named PCC-700-307, PCC-800-307, and PCC-900-307, respectively. By controlling the inherent pore size of the material itself and changing the temperature and the amount of activator added, pore size control and pore retention were achieved. At the same time, due to the abundant nitrogen content of the hydrazide group, the obtained porous carbon has considerable nitrogen atom doping.

[0093] Figure 9 (a) is the X-ray powder diffraction pattern of Poly-307. Figure 9 (b) is the infrared spectrum of Poly-307.

[0094] from Figure 9 (a) Figure 9(b) It can be seen that Poly-307 has a well-defined crystalline structure and specific acylhydrazone functional groups, which provide a good precursor basis for subsequent carbonization. As the carbonization temperature increases, the material gradually transforms from an ordered crystalline state to a partially amorphous or porous carbon material containing graphite microcrystals.

[0095] Example 7

[0096] The preparation method of Poly-305 and its derived porous carbon includes the following steps:

[0097] First, 174.2 mg of adipic hydrazide was dissolved in 10 mL of dimethyl sulfoxide and heated to 120 °C. Then, 134.1 mg of terephthalaldehyde was added, and the mixture was refluxed for 12 h while maintaining the temperature. After the reaction was complete, a white precipitate was formed. After filtration, the precipitate was washed with 3 × 10 mL of methanol and dried in an oven at 120 °C for 3 h to obtain a white powder, named Poly-305. Alternatively, 174.2 mg of adipic hydrazide was dissolved in 10 mL of dimethyl sulfoxide and heated to 120 °C. Then, 134.1 mg of terephthalaldehyde and 88.4 mg of nickel acetate were added, and the mixture was refluxed for 12 h while maintaining the temperature. After the reaction was complete, a white precipitate was formed. After filtration, the precipitate was washed with 3 × 10 mL of methanol and dried in an oven at 120 °C for 3 h to obtain a white powder, named Poly-305-Ni. Take 1g of Poly-305 powder and place it in a porcelain boat. Under a nitrogen atmosphere of 0.5L / min, carbonize it in a tube furnace at 700℃, 800℃ and 900℃ for 3h at a heating rate of 5℃ / min. Collect the black solid powder and name it PC-700-305, PC-800-305 and PC-900-305, respectively. 1 g of Poly-305 powder and 0.05 g of calcium carbonate were placed in a mortar and ground thoroughly for 30 min. The mixed powder was then placed in a porcelain boat and carbonized in a tube furnace at 700℃, 800℃, and 900℃ for 3 h at a heating rate of 5℃ / min under a nitrogen atmosphere of 0.5 L / min. The black solid powder was collected, and 30 mL of 0.1 M dilute hydrochloric acid was added and stirred for 30 min. The mixture was filtered, washed with distilled water until the filtrate was neutral, and dried in an oven at 120℃ for 3 h to obtain the black solid powder, which was named PCC-700-305, PCC-800-305, and PCC-900-305, respectively. By controlling the inherent pore size of the material itself and changing the temperature and the amount of activator added, pore size control and pore retention were achieved. At the same time, due to the abundant nitrogen content of the hydrazide group, the obtained porous carbon has considerable nitrogen atom doping.

[0098] Figure 10 (a) is the X-ray powder diffraction pattern of Poly-305. Figure 10 (b) is the infrared spectrum of Poly-305.

[0099] from Figure 10 (a) Figure 10 (b) It can be seen that Poly-305 has a well-defined crystalline structure and specific acylhydrazone functional groups, which provide a good precursor basis for subsequent carbonization. As the carbonization temperature increases, the material gradually transforms from an ordered crystalline state to a partially amorphous or porous carbon material containing graphite microcrystals.

[0100] Example 8

[0101] The preparation method of Poly-107 and its derived porous carbon includes the following steps:

[0102] First, 194.2 mg of terephthalic acid hydrazide was dissolved in 10 mL of dimethyl sulfoxide and heated to 120 °C. Then, 58.1 mg of glyoxal was added, and the mixture was refluxed for 12 h while maintaining the temperature. After the reaction was complete, a white precipitate was formed. After filtration, the precipitate was washed with 3 × 10 mL of methanol and dried in an oven at 120 °C for 3 h to obtain a white powder, named Poly-107. Alternatively, 194.2 mg of terephthalic acid hydrazide was dissolved in 10 mL of dimethyl sulfoxide and heated to 120 °C. Then, 58.1 mg of glyoxal and 88.4 mg of nickel acetate were added, and the mixture was refluxed for 12 h while maintaining the temperature. After the reaction was complete, a white precipitate was formed. After filtration, the precipitate was washed with 3 × 10 mL of methanol and dried in an oven at 120 °C for 3 h to obtain a white powder, named Poly-107-Ni. Take 1g of Poly-107 powder and place it in a porcelain boat. Under a nitrogen atmosphere of 0.5L / min, carbonize it in a tube furnace at 700℃, 800℃ and 900℃ for 3h at a heating rate of 5℃ / min. Collect the black solid powder and name it PC-700-107, PC-800-107 and PC-900-107, respectively. 1 g of Poly-107 powder and 0.05 g of calcium carbonate were placed in a mortar and ground thoroughly for 30 min. The mixed powder was then placed in a porcelain boat and carbonized in a tube furnace at 700℃, 800℃, and 900℃ for 3 h at a heating rate of 5℃ / min under a nitrogen atmosphere of 0.5 L / min. The black solid powder was collected, and 30 mL of 0.1 M dilute hydrochloric acid was added and stirred for 30 min. The mixture was filtered, washed with distilled water until the filtrate was neutral, and dried in an oven at 120℃ for 3 h to obtain the black solid powder, which was named PCC-700-107, PCC-800-107, and PCC-900-107, respectively. By controlling the inherent pore size of the material itself and changing the temperature and the amount of activator added, pore size control and pore retention were achieved. At the same time, due to the abundant nitrogen content of the hydrazide group, the obtained porous carbon has considerable nitrogen atom doping.

[0103] Figure 11 (a) is the X-ray powder diffraction pattern of Poly-107. Figure 11(b) is the infrared spectrum of Poly-107.

[0104] from Figure 11 (a) Figure 11 (b) It can be seen that Poly-107 has a well-defined crystalline structure and specific acylhydrazone functional groups, which provide a good precursor basis for subsequent carbonization. As the carbonization temperature increases, the material gradually transforms from an ordered crystalline state to a partially amorphous or porous carbon material containing graphite microcrystals.

[0105] Example 9

[0106] The preparation method of Poly-207 and its derived porous carbon includes the following steps:

[0107] First, 194.2 mg of terephthalic acid hydrazide was dissolved in 10 mL of dimethyl sulfoxide and heated to 120 °C. Then, 100.2 mg of glutaraldehyde was added, and the mixture was refluxed for 12 h while maintaining the temperature. After the reaction was complete, a white precipitate was formed. After filtration, the precipitate was washed with 3 × 10 mL of methanol and dried in an oven at 120 °C for 3 h to obtain a white powder, named Poly-207. Alternatively, 194.2 mg of terephthalic acid hydrazide was dissolved in 10 mL of dimethyl sulfoxide and heated to 120 °C. Then, 100.2 mg of glutaraldehyde and 88.4 mg of nickel acetate were added, and the mixture was refluxed for 12 h while maintaining the temperature. After the reaction was complete, a white precipitate was formed. After filtration, the precipitate was washed with 3 × 10 mL of methanol and dried in an oven at 120 °C for 3 h to obtain a white powder, named Poly-207-Ni. Take 1g of Poly-207 powder and place it in a porcelain boat. Under a nitrogen atmosphere of 0.5L / min, carbonize it in a tube furnace at 700℃, 800℃ and 900℃ for 3h at a heating rate of 5℃ / min. Collect the black solid powder and name it PC-700-207, PC-800-207 and PC-900-207, respectively. 1 g of Poly-207 powder and 0.05 g of calcium carbonate were placed in a mortar and ground thoroughly for 30 min. The mixed powder was then placed in a porcelain boat and carbonized in a tube furnace at 700℃, 800℃, and 900℃ for 3 h at a heating rate of 5℃ / min under a nitrogen atmosphere of 0.5 L / min. The black solid powder was collected, and 30 mL of 0.1 M dilute hydrochloric acid was added and stirred for 30 min. The mixture was filtered, washed with distilled water until the filtrate was neutral, and dried in an oven at 120℃ for 3 h to obtain the black solid powder, which was named PCC-700-207, PCC-800-207, and PCC-900-207, respectively. By controlling the inherent pore size of the material itself and changing the temperature and the amount of activator added, pore size control and pore retention were achieved. At the same time, due to the abundant nitrogen content of the hydrazide group, the obtained porous carbon has considerable nitrogen atom doping.

[0108] Figure 12(a) is the X-ray powder diffraction pattern of Poly-207. Figure 12 (b) is the infrared spectrum of Poly-207.

[0109] from Figure 12 (a) Figure 12 (b) It can be seen that Poly-207 has a well-defined crystalline structure and specific acylhydrazone functional groups, which provide a good precursor basis for subsequent carbonization. As the carbonization temperature increases, the material gradually transforms from an ordered crystalline state to a partially amorphous or porous carbon material containing graphite microcrystals.

[0110] Example 10

[0111] The performance testing of HC-700-101, HC-800-101, and HC-900-101 as positive electrodes for zinc-iodine batteries includes the following steps:

[0112] HC-700-101, HC-800-101, and HC-900-101 were mixed with Ketjen Black and polyvinylidene fluoride in a mass ratio of 7:2:1, respectively. An appropriate amount of N-methylpyrrolidone was added dropwise to the mixture until it became a homogeneous slurry. This slurry was then uniformly coated onto a clean steel foil and dried in an oven at 80°C for 12 hours to obtain the corresponding cathode material. For testing, the cathode material was cut into pieces with an area of ​​approximately 5.3 cm². 2 The discs were used as negative electrodes, and a zinc sheet polished with sandpaper was used as the negative electrode. A mixed solution of 3M zinc sulfate and 0.5M potassium iodide was used as the electrolyte. Together with a cellulose separator, they were assembled into a CR2032 button cell and subjected to long charge-discharge cycle tests.

[0113] Figure 13 (a) is a graph showing the long-cycle battery performance of HC-900-101.

[0114] from Figure 13 (a) It can be seen that HC-900-101 maintains a high specific capacity with minimal fluctuations during multiple charge-discharge cycles, indicating that the material has good cycle stability and a long cycle life. The coulombic efficiency is close to 100%, indicating that HC-900-101 has excellent electrochemical reversibility and a low rate of side reactions. This demonstrates that the battery can significantly suppress the iodine shuttle effect during use, exhibiting high specific capacity and excellent cycle stability.

[0115] Example 11

[0116] The performance testing of HCC-700-101, HCC-800-101, and HCC-900-101 as positive electrodes for zinc-iodine batteries includes the following steps:

[0117] HCC-700-101, HCC-800-101, and HCC-900-101 were mixed with Ketjen Black and polyvinylidene fluoride in a mass ratio of 7:2:1, respectively. An appropriate amount of N-methylpyrrolidone was added dropwise to the mixture until it became a homogeneous slurry. This slurry was then uniformly coated onto a clean steel foil and dried in an oven at 80°C for 12 hours to obtain the corresponding cathode material. For testing, the cathode material was cut into pieces with an area of ​​approximately 5.3 cm². 2 The discs were used as negative electrodes, and a zinc sheet polished with sandpaper was used as the negative electrode. A mixed solution of 3M zinc sulfate and 0.5M potassium iodide was used as the electrolyte. Together with a cellulose separator, they were assembled into a CR2032 button cell and subjected to long charge-discharge cycle tests.

[0118] Figure 13 (b) shows the long-cycle battery performance of HCC-900-101. From... Figure 13 (b) It can be seen that HCC-900-101 maintains a high specific capacity level and is superior to HC-900-101 during multiple charge-discharge cycles, with less fluctuation, indicating that this material has good cycle stability. Adding a small amount of activator can significantly improve battery performance and achieve a long cycle life. The coulombic efficiency is close to 100%, indicating that HCC-900-101 has excellent electrochemical reversibility and a low side reaction rate. This shows that it can significantly suppress the iodine shuttle effect during battery use, exhibiting high specific capacity and excellent cycle stability.

[0119] Figure 14 This section shows the pore distribution and corresponding pore areas for HC-700-101, HC-800-101, HC-900-101, and HCC-900-101. From... Figure 14 It can be seen that HC-700-101, HC-800-101, HC-900-101 and HCC-900-101 all have a multi-level pore structure of micropores and mesopores, and the pore area gradually increases with the increase of carbonization temperature; adding a small amount of activator can promote the formation of a large number of channels.

[0120] Figure 15 Full XPS spectra for HC-700-101, HC-800-101, and HC-900-101. From Figure 15 It can be seen that HC-700-101, HC-800-101 and HC-900-101 all have considerable nitrogen atom doping.

[0121] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A flexible acylhydrazone hydrogen-bonded framework, characterized in that, The structural formula of the flexible acylhydrazone hydrogen bonding framework is shown in any of the following examples:

2. A method for preparing a flexible acylhydrazone hydrogen-bonded framework according to claim 1, characterized in that, Includes the following steps: The dihydrazide raw material is dissolved in a solvent, heated, and then diacetyl raw material is added. A catalyst may or may not be added as needed. The product is obtained by refluxing while maintaining a constant temperature.

3. The method for preparing the flexible acylhydrazone hydrogen-bonded framework according to claim 2, characterized in that, The diacetyl raw material includes any one of 2,6-diacetylpyridine, 2,6-dimethyl-3,5-diacetylpyridine, 2,4,6-trimethyl-3,5-diacetylpyridine, N,9-diacetylguanine, and 1,3-diacetylbenzene; The dihydrazide raw materials include any one of the following: carbazide, oxaloyl dihydrazide, malonyl dihydrazide, succinic dihydrazide, glutaryl dihydrazide, adipic dihydrazide, dodecyl dihydrazide, terephthalic dihydrazide, 4,4'-biphenyl dicarboxylic acid dihydrazide, 2,6-naphthalenedicarboxylic acid dihydrazide, thiodi(acetylhydrazide), 2,5-thiophenic acid dihydrazide, octafluoroadipate dihydrazide, trans, trans-2,4-hexadiene dichydrazide, 1,2-ethylidene di(carbamoyl hydrazide), 1,2-ethylidene bis(hydrazine), 1,3-propylidene bis(hydrazine), and 1,4-butylidene bis(hydrazine). The catalyst comprises a metal salt, which includes one of nickel sulfate, nickel chloride, nickel perchlorate, nickel nitrate, nickel acetate, copper sulfate, copper chloride, copper perchlorate, copper nitrate, and copper acetate.

4. A flexible acylhydrazone-based polymer material, characterized in that, The structural formula of the flexible acylhydrazone polymer material is shown in any of the following examples: The degree of polymerization n is 10 to 30.

5. The method for preparing the flexible acylhydrazone-based polymer material according to claim 4, characterized in that, Includes the following steps: The dihydrazide raw material is dissolved in a solvent, heated, and then a dialdehyde raw material is added. A catalyst may or may not be added as needed. The corresponding product is obtained by refluxing while maintaining a constant temperature.

6. The preparation method according to claim 5, characterized in that, The dialdehyde-based raw material includes any one of isophthalaldehyde, 2,6-pyridinedialdehyde, glyoxal, glutaraldehyde, and terephthalaldehyde; The dihydrazide raw material includes any one of carbazide, oxaloyl dihydrazide, malonyl dihydrazide, succinic dihydrazide, glutaryl dihydrazide, adipic dihydrazide, dodecyl dihydrazide, terephthalic dihydrazide, and 4,4'-biphenyl dihydrazide; The catalyst comprises a metal salt, which includes one of nickel sulfate, nickel chloride, nickel perchlorate, nickel nitrate, nickel acetate, copper sulfate, copper chloride, copper perchlorate, copper nitrate, and copper acetate.

7. A porous carbon material, characterized in that, It is prepared from the flexible acylhydrazone hydrogen bonding framework of claim 1 or the flexible acylhydrazone polymer material of claim 4 as raw materials.

8. The porous carbon material according to claim 7, characterized in that, The flexible acylhydrazone hydrogen-bonded framework or the flexible acylhydrazone polymer material is placed in a ceramic boat, and a pore-forming agent is selectively added or not added. The pore-forming agent is one or more of potassium hydroxide, potassium carbonate, potassium bicarbonate, calcium carbonate, sodium hydroxide, sodium carbonate, and sodium bicarbonate, and the addition amount is 5% to 20%. Subsequently, it is carbonized at high temperature in a tube furnace under an inert gas atmosphere. The carbonization temperature is 700 to 900°C, the heating rate is 3 to 10°C / min, and the carbonization time is 1 to 5 hours to obtain the corresponding porous carbon material product.

9. The application of the porous carbon material according to claim 7 or 8 in the preparation of aqueous zinc-iodine batteries.

10. The application according to claim 9, characterized in that, The porous carbon material was used to prepare a positive electrode for use in an aqueous zinc-iodine battery.

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