High-energy-density imidazoline polymer electrode material and preparation method thereof
The preparation of imidazoline polymer electrode materials by solvent thermal method solves the problem of low energy density of supercapacitor electrode materials, and achieves the application of electrode materials with high energy density and good light absorption performance, replacing traditional carbon materials as the electrode positive electrode.
Patent Information
- Application Number
- CN202510634365.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-16
- Publication Date
- 2025-08-15
AI Technical Summary
The energy density of existing supercapacitor electrode materials is not high, the energy storage performance is not satisfactory, and the stability is poor. It is necessary to develop new materials with high energy density and high cycle stability.
A high-energy density imidazoline polymer electrode material was prepared by solvothermal method. By selecting dialdehyde monomer and inorganic ammonium salt reacted in solvent, a uniform mixed solution was formed, and a solvothermal reaction was carried out. After filtration and drying, a pure imidazoline polymer electrode material was obtained.
The prepared imidazoline polymer electrode material exhibits high energy density and good light absorption properties in asymmetric supercapacitors, which is easy to promote and use, replacing traditional carbon materials as electrode positive electrode materials.
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Figure CN120497058A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the synthesis and energy storage application fields of imidazoline polymers, and in particular to high-energy-density imidazoline polymer electrode materials, preparation methods, and applications thereof. Background Art
[0002] Supercapacitors are a new type of energy storage device, offering advantages such as fast charge and discharge rates, long cycle life, and a clean, environmentally friendly design. The growing demand for energy storage systems with high power density, rapid charge / discharge capabilities, and long cycle life has driven extensive research into advanced materials for supercapacitor applications. Among these materials, conductive polymers, with their highly reversible redox behavior—a property shared by plastics and metals—are promising candidates for their superior environmental stability, economic relevance, increased stability, reduced weight, improved workability, corrosion resistance, and excellent electrical conductivity.
[0003] Currently, polyaniline, polypyrrole, polythiophene, and their derivatives have been widely used as supercapacitor electrode materials due to their significant pseudocapacitance, high conductivity, and affordability. However, the energy storage performance of these pseudocapacitive materials remains unsatisfactory, including insufficient energy density, the need for further research into the energy storage mechanism, and poor stability. There is a need to develop supercapacitor electrode materials with high energy density, high power density, and high cycling stability. Summary of the Invention
[0004] The technical problem to be solved by the present invention is to overcome the above technical defects and provide a high-energy-density imidazoline polymer electrode material and its preparation method that has a wide range of applications including: secondary battery energy storage, supercapacitor light and electrochemical energy storage, and solar cell material energy storage.
[0005] To solve the above technical problems, the present invention provides a technical solution: a method for preparing a high energy density imidazoline polymer electrode material, comprising the following steps:
[0006] S1: selecting a dialdehyde monomer, an inorganic ammonium salt and a solvent to form a uniform mixed solution;
[0007] S2: transferring the mixed solution prepared in S1 to a high-pressure reactor for solvothermal reaction to obtain a suspension of imidazoline polymer;
[0008] S3: filtering and extracting the suspension obtained in S2 to obtain pure imidazoline polymer;
[0009] S4: Drying the purified imidazoline polymer to obtain the electrode material.
[0010] Preferably, the dialdehyde monomer in S1 includes one or a combination of terephthalaldehyde, 2-hydroxyterephthalaldehyde, 2,5-dibromoterephthalaldehyde, isophthalaldehyde, pyrazine-2,5-dicarboxaldehyde, naphthalene-1,4-dicarboxaldehyde, 9,10-anthracene dicarboxaldehyde,
[0011] Inorganic ammonium salts include one or a combination of ammonium carbonate, ammonium sulfate, ammonium acetate, and ammonium halides;
[0012] The solvent includes any one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), triethanolamine (TEA), glycerol (GL), dichloromethane (DCM) or chloroform.
[0013] Preferably, the molar ratio of the dialdehyde monomer to the inorganic ammonium salt in S1 is 1-4.
[0014] Preferably, the solvent thermal reaction temperature in S2 is in the range of 100 to 180° C., and the reaction time is 10 to 48 hours.
[0015] Preferably, the washing and extraction solvent in S3 includes any one of anhydrous ethanol, tetrahydrofuran, and dichloromethane.
[0016] Preferably, the drying temperature in S4 is 60-80° C. and the drying time is 6-24 hours.
[0017] Preferably, the solid filter cake obtained by filtration in S3 is washed and extracted using a Soxhlet extractor.
[0018] Another aspect of the present invention discloses a high energy density imidazoline polymer electrode material prepared by the above method.
[0019] Another aspect of the present invention discloses the application of high energy density imidazoline polymer electrode materials in three electrodes, when one of the polymers is at a current density of 1Ag -1 When the specific capacitance value ranges from 2000 to 3500 F g -1 .
[0020] Another aspect of the present invention discloses the application of high energy density imidazoline polymer electrode materials in supercapacitors, when one of the polymers is at a current density of 1Ag -1 When the asymmetric specific capacitance value ranges from 150 to 200F-1g.
[0021] The advantages of the present invention over the prior art are that: the present invention does not use traditional carbon materials as electrode positive materials, but instead synthesizes a new type of organic polymer as electrode positive material. When this positive electrode material is assembled into an asymmetric supercapacitor, it can achieve high energy density and has good light absorption performance, and is easy to promote and use. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 This is a SEM image of the polymer prepared in Example 1 of the present invention.
[0023] Figure 2 This is the UV-visible diffuse reflectance spectrum of the polymer prepared in Example 1 of the present invention.
[0024] Figure 3 This is a graph showing the electrochemical performance of an asymmetric supercapacitor assembled using the polymer prepared in Example 1 of the present invention as a positive electrode material in a 6M KOH electrolyte. DETAILED DESCRIPTION
[0025] The present invention will be described in further detail below with reference to the accompanying drawings.
[0026] Combined with attachment Figure 1-3 shown.
[0027] Example 1
[0028] 2.00 g of terephthalaldehyde and 3.19 g of ammonium chloride were mixed in 45 ml of NN-dimethylformamide solvent and stirred for 2 hours to form a mixed solution. The mixed solution was transferred to a polytetrafluoroethylene-lined solvothermal reactor and reacted at 150°C for 48 hours. After cooling to room temperature, a suspension of imidazoline polymer was obtained. The solid filter cake was filtered and washed with tetrahydrofuran and then ethanol in a Soxhlet extractor to obtain pure imidazoline polymer. The product was dried at 60°C and named IP-Cl.
[0029] Example 2
[0030] Mix 2.00 g of isophthalaldehyde and 3.19 g of ammonium chloride in 45 ml of N-dimethylformamide solvent and stir for 2 hours to form a mixed solution. Transfer the mixed solution to a polytetrafluoroethylene-lined solvothermal reactor and react at 150°C for 48 hours. After cooling to room temperature, a suspension of imidazoline polymer is obtained. Filter the suspension, and the solid filter cake is washed and extracted in a Soxhlet extractor with tetrahydrofuran and then ethanol to obtain a pure imidazoline polymer, which is then dried at 60°C.
[0031] Example 3
[0032] Mix 2.00 g of terephthalaldehyde and 5.84 g of ammonium bromide in 45 ml of triethanolamine solvent and stir for 2 hours to form a mixed solution. Transfer the mixed solution to a polytetrafluoroethylene-lined solvent thermal reactor and react at 150°C for 48 hours. After cooling to room temperature, a suspension of imidazoline polymer is obtained. Filter the suspension, and the solid filter cake is washed and extracted in a Soxhlet extractor with tetrahydrofuran and then ethanol to obtain a pure imidazoline polymer, which is then dried at 60°C.
[0033] Example 4
[0034] Mix 2.00 g of terephthalaldehyde and 7.88 g of ammonium sulfate in 45 ml of glycerol solvent and stir for 2 hours to form a mixed solution. Transfer the mixed solution to a polytetrafluoroethylene-lined solvent thermal reactor and react at 150°C for 48 hours. After cooling to room temperature, a suspension of imidazoline polymer is obtained. Filter the suspension, and the solid filter cake is washed and extracted in a Soxhlet extractor with tetrahydrofuran and then ethanol to obtain a pure imidazoline polymer, which is then dried at 60°C.
[0035] Example 5
[0036] Mix 2.74 g of naphthalene-1,4-dicarboxaldehyde and 7.88 g of ammonium sulfate in 45 ml of NN-dimethylacetamide solvent and stir for 2 hours to form a mixed solution. The mixed solution was transferred to a polytetrafluoroethylene-lined solvothermal reactor and reacted at 150°C for 48 hours. After cooling to room temperature, a suspension of imidazoline polymer was obtained. The solid filter cake was then washed and extracted in a Soxhlet extractor with tetrahydrofuran and then ethanol to obtain a pure imidazoline polymer, which was then dried at 60°C.
[0037] Example 6
[0038] Mix 2.74 g of naphthalene-1,4-dicarboxaldehyde and 7.88 g of ammonium sulfate in 45 ml of N-dimethylformamide solvent and stir for 2 hours to form a mixed solution. The mixed solution was transferred to a polytetrafluoroethylene-lined solvothermal reactor and reacted at 150°C for 48 hours. After cooling to room temperature, a suspension of imidazoline polymer was obtained. The solid filter cake was then washed and extracted in a Soxhlet extractor with tetrahydrofuran and then ethanol to obtain a pure imidazoline polymer, which was then dried at 60°C.
[0039] Example 7
[0040] Mix 2.74 g of naphthalene-1,4-dicarboxaldehyde and 2.21 g of ammonium fluoride in 45 ml of N-dimethylformamide solvent and stir for 2 hours to form a mixed solution. The mixed solution was transferred to a polytetrafluoroethylene-lined solvothermal reactor and reacted at 150°C for 48 hours. After cooling to room temperature, a suspension of imidazoline polymer was obtained. The solid filter cake was then washed and extracted in a Soxhlet extractor with tetrahydrofuran and then ethanol to obtain a pure imidazoline polymer, which was then dried at 60°C.
[0041] Example 8
[0042] Mix 2.00 g of paraformaldehyde and 2.21 g of ammonium fluoride in 45 ml of triethanolamine solvent and stir for 2 hours to form a mixed solution. Transfer the mixed solution to a polytetrafluoroethylene-lined solvothermal reactor and react at 150°C for 48 hours. After cooling to room temperature, a suspension of imidazoline polymer is obtained. Filter the suspension, and the solid filter cake is washed and extracted in a Soxhlet extractor with tetrahydrofuran and then ethanol to obtain a pure imidazoline polymer, which is then dried at 60°C.
[0043] Example 9
[0044] Mix 2.00 g of paraformaldehyde and 3.19 g of ammonium chloride in 45 ml of triethanolamine solvent and stir for 2 hours to form a mixed solution. Transfer the mixed solution to a polytetrafluoroethylene-lined solvothermal reactor and react at 150°C for 48 hours. After cooling to room temperature, a suspension of imidazoline polymer is obtained. Filter the suspension, and the solid filter cake is washed and extracted in a Soxhlet extractor with tetrahydrofuran and then ethanol to obtain a pure imidazoline polymer, which is then dried at 60°C.
[0045] Example 10
[0046] Mix 2.00 g of paraformaldehyde and 3.19 g of ammonium chloride in 45 ml of glycerol solvent and stir for 2 hours to form a mixed solution. Transfer the mixed solution to a polytetrafluoroethylene-lined solvothermal reactor and react at 150°C for 48 hours. After cooling to room temperature, a suspension of imidazoline polymer is obtained. Filter the suspension, and the solid filter cake is washed and extracted in a Soxhlet extractor with tetrahydrofuran and then ethanol to obtain a pure imidazoline polymer, which is then dried at 60°C.
[0047] Example 11
[0048] Mix 2.00 g of paraformaldehyde and 8.64 g of ammonium iodide in 45 ml of glycerol solvent and stir for 2 hours to form a mixed solution. Transfer the mixed solution to a polytetrafluoroethylene-lined solvothermal reactor and react at 150°C for 48 hours. After cooling to room temperature, a suspension of imidazoline polymer is obtained. Filter the suspension, and the solid filter cake is washed and extracted in a Soxhlet extractor with tetrahydrofuran and then ethanol to obtain a pure imidazoline polymer, which is then dried at 60°C.
[0049] Example 12
[0050] Mix 2.00 g of paraformaldehyde and 4.60 g of ammonium acetate in 45 ml of NN-dimethylacetamide solvent and stir for 2 hours to form a mixed solution. Transfer the mixed solution to a polytetrafluoroethylene-lined solvothermal reactor and react at 150°C for 48 hours. After cooling to room temperature, a suspension of imidazoline polymer is obtained. Filter the suspension, and the solid filter cake is washed and extracted in a Soxhlet extractor with tetrahydrofuran and then ethanol to obtain a pure imidazoline polymer, which is then dried at 60°C.
[0051] The present invention and its embodiments are described above. This description is not restrictive. The drawings show only one embodiment of the present invention, and the actual structure is not limited thereto. In short, if a person skilled in the art is inspired by this and, without departing from the purpose of the present invention, designs structures and embodiments similar to this technical solution without inventiveness, they shall fall within the scope of protection of the present invention.
Claims
1. A method for preparing a high energy density imidazoline polymer electrode material, characterized in that: The steps include: S1: selecting a dialdehyde monomer, an inorganic ammonium salt and a solvent to form a uniform mixed solution; S2: transferring the mixed solution prepared in S1 to a high-pressure reactor for solvothermal reaction to obtain a suspension of imidazoline polymer; S3: filtering and extracting the suspension obtained in S2 to obtain pure imidazoline polymer; S4: Drying the purified imidazoline polymer to obtain the electrode material.
2. The method for preparing a high energy density imidazoline polymer electrode material according to claim 1, wherein: The dialdehyde monomer in S1 includes one or a combination of terephthalaldehyde, 2-hydroxyterephthalaldehyde, 2,5-dibromoterephthalaldehyde, isophthalaldehyde, pyrazine-2,5-dicarboxaldehyde, naphthalene-1,4-dicarboxaldehyde, 9,10-anthracene dicarboxaldehyde, etc. Inorganic ammonium salts include one or a combination of ammonium carbonate, ammonium sulfate, ammonium acetate, and ammonium halides; The solvent includes any one of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), triethanolamine (TEA), glycerol (GL), dichloromethane (DCM) or chloroform.
3. The method for preparing a high energy density imidazoline polymer electrode material according to claim 1 or 2, characterized in that: The molar ratio of the dialdehyde monomer to the inorganic ammonium salt in S1 is 1-4.
4. The method for preparing a high energy density imidazoline polymer electrode material according to claim 1, wherein: The solvent thermal reaction temperature in S2 is in the range of 100 to 180° C., and the reaction time is 10 to 48 hours.
5. The method for preparing a high energy density imidazoline polymer electrode material according to claim 1, wherein: The washing and extraction solvent in S3 includes any one of anhydrous ethanol, tetrahydrofuran, and dichloromethane.
6. The method for preparing a high energy density imidazoline polymer electrode material according to claim 1, characterized in that: The drying temperature in S4 is 60-80° C. and the drying time is 6-24 hours.
7. The method for preparing a high energy density imidazoline polymer electrode material according to claim 5, characterized in that: The solid filter cake is obtained by filtration in S3 and washed and extracted using a Soxhlet extractor.
8. A high energy density imidazoline polymer electrode material prepared according to the method of any one of claims 1 to 7.
9. The application of the high energy density imidazoline polymer electrode material in three electrodes according to claim 8, when one of the polymers is subjected to a current density of 1Ag -1 When the specific capacitance value ranges from 2000 to 3500 F g -1 .
10. Application of the high energy density imidazoline polymer electrode material in supercapacitors according to claim 8, wherein one of the polymers is -1 When the asymmetric specific capacitance value ranges from 150 to 200F g -1 .