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CN-121991097-A - Conjugated imidazole organic electrode material and preparation method and application thereof

CN121991097ACN 121991097 ACN121991097 ACN 121991097ACN-121991097-A

Abstract

The invention belongs to the field of electrode materials of water-based ion batteries, and particularly relates to a conjugated imidazole organic electrode material, a preparation method and application thereof. The invention provides a conjugated imidazole compound which contains a plurality of redox active sites, so that the conjugated imidazole compound has higher theoretical capacity. When the conjugated imidazole compound is used as an electrode material of a water-based ion battery, the conjugated imidazole compound realizes high specific capacity and excellent rate performance and cycle stability. The conjugated imidazole compound improves the capacity of organic electrode materials of the ion battery, has the advantages of low unit cost, long cycle life, safety, environmental protection and the like, and has wide application prospect in the aspect of high-energy-density energy storage batteries.

Inventors

  • XU JUAN
  • ZHOU GUANGHUI
  • CAO JIANYU

Assignees

  • 常州大学

Dates

Publication Date
20260508
Application Date
20260114

Claims (10)

  1. 1. The preparation method of the conjugated imidazole organic electrode material is characterized by comprising the following steps of: (1) Adding an aqueous solution containing ferric trichloride into an o-phenylenediamine aqueous solution, vigorously stirring at 50 ℃ until the color changes from black to red, standing, pouring out supernatant, repeating the process for 4 times, filtering and separating red precipitate, washing with deionized water to ensure removal of iron ions, and then placing the product in a70 ℃ drying oven for vacuum drying to obtain red powder which is an intermediate 2, 3-diaminophenazine DAP; (2) Dissolving DAP and benzaldehyde or its derivative in organic solvent, ultrasonic vibration, reflux heating in oil bath under nitrogen protection, filtering the reaction liquid after reaction, washing with ethanol and water until the filtrate is colorless, vacuum drying for 4 hr, taking out the dried product, reflux heating with 30wt.% nitric acid, filtering while hot after reaction, washing with water and ethanol until the filtrate is colorless, vacuum drying for 4 hr, recrystallizing with DMF, filtering, and oven drying overnight to obtain 2-phenyl-1H-imidazo [4,5-b ] phenazine (PIP) or its derivative.
  2. 2. The method for preparing a conjugated imidazole organic electrode material according to claim 1, wherein in the step (1), the molar ratio of ferric trichloride to o-phenylenediamine is 0.08:0.1.
  3. 3. The method for preparing a conjugated imidazole organic electrode material according to claim 1, wherein in the step (2), benzaldehyde or a derivative thereof is selected from the group consisting of benzaldehyde, terephthalaldehyde, trimellitic aldehyde, 2-methyl-benzaldehyde, 3-methyl-benzaldehyde, 4-methyl-benzaldehyde, 2, 3-dimethyl-benzaldehyde, 2, 4-dimethyl-benzaldehyde, 2, 5-dimethyl-benzaldehyde, 2, 6-dimethyl-benzaldehyde, 3, 4-dimethyl-benzaldehyde, 3, 5-dimethyl-benzaldehyde, 1, 4-benzaldehyde, 2-methyl-1, 4-benzaldehyde, 2, 5-dimethyl-1, 4-benzaldehyde, 2,3,5, 6-tetramethyl-1, 4-benzaldehyde, 1,3, 5-benzaldehyde, 2,4, 6-trimethyl-1, 3, 5-benzaldehyde, 2,4, 6-trichloro-1, 5-benzaldehyde.
  4. 4. The method for preparing a conjugated imidazole organic electrode material according to claim 1, wherein in the step (2), the molar ratio of DAP to benzaldehyde or a derivative thereof is 1:1-3:1, and the organic solvent is N-methyl-2-pyrrolidone, dimethyl sulfoxide or N, N-dimethylformamide.
  5. 5. The method for producing a conjugated imidazole organic electrode material according to claim 1, wherein in the step (2), the heating temperature of the oil bath is 80 ℃ to 160 ℃, and the reflux reaction time is 3 h to 72 h.
  6. 6. The conjugated imidazole organic electrode material prepared by the method according to claim 1, wherein the conjugated imidazole organic electrode material is selected from one of the following three types of compounds: , Wherein R 1 -R 5 is selected from 0-2 of methyl and chloro.
  7. 7. The use of the conjugated imidazole organic electrode material prepared by the method according to claim 1, wherein the conjugated imidazole organic electrode material is used as a positive electrode material of an aqueous zinc ion battery.
  8. 8. The application of the conjugated imidazole organic electrode material according to claim 7, wherein the conjugated imidazole organic electrode material, the conductive additive and the adhesive are uniformly dispersed in a solvent and coated on a current collector, and the water-based zinc ion battery anode material is obtained by vacuum drying, cutting into slices and packaging into a battery.
  9. 9. The application of the conjugated imidazole organic electrode material according to claim 8, wherein the mass ratio of the conjugated imidazole organic electrode material to the conductive additive to the binder is 3-9:1-6:0-1.
  10. 10. The application of the conjugated imidazole organic electrode material according to claim 8, wherein the conductive additive is carbon black, super P, ketjen black, active carbon, graphene or carbon nano tube, the adhesive is polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol or styrene-butadiene rubber, the current collector is 300 mesh stainless steel mesh, titanium mesh, carbon paper, aluminum foil or copper foil, the vacuum drying temperature is 60-110 ℃, and the drying time is 4-18 h.

Description

Conjugated imidazole organic electrode material and preparation method and application thereof Technical Field The invention belongs to the field of electrode materials of water-based ion batteries, and particularly relates to a conjugated imidazole organic electrode material, a preparation method and application thereof. Background Along with the acceleration transformation of global energy structures to renewable energy sources represented by wind energy and solar energy, the development of large-scale, low-cost and high-safety electrochemical energy storage technologies has become a key point for guaranteeing the stable operation of a power grid. Under the background, the water-based zinc ion battery is regarded as an important development direction for replacing the existing lithium battery technology in the field of large-scale energy storage by virtue of the outstanding advantages of intrinsic safety, abundant resources, environmental friendliness and low cost. Currently, a core bottleneck that restricts further improvement of the performance of zinc ion batteries is mainly the cathode material. Although the most widely studied inorganic positive electrode materials (such as manganese-based oxide and vanadium-based oxide) show a certain capacity potential, the inherent crystal structure of the inorganic positive electrode materials is easy to generate irreversible phase change and collapse in the repeated embedding/extracting process of Zn 2+, so that the capacity is fast attenuated, and meanwhile, the problems of dissolution loss of the materials in a water-based electrolyte (such as manganese dissolution) and the toxicity limitation of partial elements (such as vanadium) seriously influence the cycle life and the environmental compatibility of the battery. More critical is that the narrow ion channel in the rigid crystal structure of the material limits the rapid migration of Zn 2+ and restricts the rate capability of the battery. In comparison, the organic positive electrode material utilizes active functional groups such as carbonyl, imine and the like to carry out efficient and reversible coordination reaction with Zn 2+ through molecular design, thereby providing a brand new path for solving the problems. The flexible molecular skeleton can effectively buffer stress caused by ion intercalation/deintercalation, has better structural stability and longer circulating potential, can accurately regulate and control electrochemical performance (such as voltage and capacity) due to designability of a molecular structure, and meanwhile, is mainly composed of C, H, O, N and other elements, and is sustainable in resource acquisition and small in environmental burden. However, the low intrinsic conductivity of the organic material itself and the tendency to dissolve in the electrolyte remain challenges that must be overcome for its industrial application. Therefore, development of a novel efficient organic positive electrode material is needed, which can effectively solve the problems of insufficient conductivity and solubility of the material through innovative material design and structural optimization on the basis of fully exerting inherent advantages of the material, such as structural flexibility, sustainable resources, designability of molecules and the like, so as to provide an advanced and reliable positive electrode solution for constructing next-generation high-performance and long-service-life zinc ion batteries. Disclosure of Invention The invention aims to provide a conjugated imidazole organic electrode material, a preparation method thereof and application thereof in a zinc ion battery, so as to solve the problems of low capacity and poor cycle stability of an inorganic electrode material in the past. The conjugated imidazole organic electrode material is one of the following three compounds: 。 Wherein R 1-R5 is selected from 0-2 of methyl and chloro. The conjugated imidazole organic electrode material is used as an organic positive electrode material of a zinc ion battery, and abundant C=N active sites in molecules endow the material with high theoretical specific capacity for realizing multi-electron reversible reaction, and a highly stable conjugated framework and a reversible coordination energy storage mechanism fundamentally ensure the excellent structural stability and the ultra-long cycle life of the material. Meanwhile, the extended conjugated system not only provides an ideal channel for intrinsic electron conduction, but also creates favorable conditions for rapid transport of zinc ions by virtue of an open molecular configuration, so that the material has excellent rate capability. In addition, the material is completely composed of light elements (C, H, N) with wide sources, abandons expensive or toxic metal resources, has the remarkable advantages of low cost and environmental friendliness, and has wide application prospect in the aspect of high-energy-density energy storage b