Conjugated macrocyclic polymer-based electrode material, and preparation method and application thereof

Abstract

The application discloses an electrode material based on a conjugated macrocyclic polymer and a preparation method and application thereof, and belongs to the technical field of battery materials, wherein the electrode material is a conjugated macrocyclic polymer obtained by condensation polymerization of a columnar arene derivative containing an acyl group and an N,N,N',N'-tetra-(p-aminophenyl)-p-phenylenediamine ligand through a Schiff base reaction. The electrode material based on the conjugated macrocyclic polymer can be used in the field of organic zinc ion aqueous batteries in actual application. The electrode material breaks through the performance limitation of traditional electrode materials through the synergistic effect of the faradic and non-faradic dual-state energy storage modes, and provides higher energy storage efficiency and a longer service life. In addition, the electrode material can not only improve the rate performance of a battery under different current densities, but also effectively prolong the cycle life of the battery, and has excellent electrochemical performance and stability.

Description

Technical Field

[0001] This invention relates to the field of battery materials technology, specifically to an electrode material based on a conjugated macrocyclic polymer, its preparation method, and its application. Background Technology

[0002] With increasing global focus on sustainable energy and environmentally friendly technologies, organic zinc-ion batteries, as a novel energy storage technology, have gradually become a hot topic in battery research. Especially in aqueous battery systems, organic zinc-ion batteries have been widely used due to their lower environmental pollution and higher safety. However, existing organic zinc-ion battery cathode materials still have certain shortcomings in terms of specific capacitance, failing to meet the demands of high-performance batteries. Traditional organic zinc-ion battery cathode materials mostly rely on organic compounds as active materials. Although these materials have high energy density, their electrochemical performance, especially in terms of specific capacitance, is usually limited. To address this issue, many researchers have attempted to improve battery performance through different chemical modifications or composite materials, but these methods often face challenges such as poor material stability, complex preparation processes, and high costs.

[0003] The disadvantages of existing organic zinc-ion battery cathode materials are: (1) Low specific capacitance, making it difficult to meet the requirements of high-performance batteries; traditional organic zinc-ion battery cathode materials mainly rely on Faraday reactions for the storage and release of zinc ions. However, the lack of sufficient ion storage sites makes these materials significantly limited in terms of improving specific capacitance. (2) Poor material stability and short cycle life; existing organic zinc-ion battery cathode materials are easily affected by the external environment during long-term use, leading to material degradation and performance decline, resulting in poor battery stability and affecting the long-term use of the battery. (3) Complex preparation process and high cost; the preparation process of many existing organic zinc-ion battery cathode materials involves complex chemical modifications and high-cost raw materials, which increases the cost of battery production and limits its large-scale application.

[0004] In summary, most existing organic zinc-ion battery cathode materials rely on a single Faradaic reaction for the storage and release of zinc ions, lacking sufficient ion storage sites to effectively improve the battery's specific capacitance. To overcome these limitations, researchers have attempted to increase the battery's energy storage capacity by introducing materials with Faradaic active sites. However, this approach often overlooks the crucial role of the non-Faraday effect in improving battery performance. Summary of the Invention

[0005] The purpose of this invention is to provide an electrode material based on a conjugated macrocyclic polymer, its preparation method, and its application, in order to solve the problems mentioned in the background art.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] An electrode material based on a conjugated macrocyclic polymer is a conjugated macrocyclic polymer formed by the condensation polymerization of an acyl-containing columnar aromatic derivative and an N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine ligand via a Schiff base reaction.

[0008] Furthermore, the general structural formula of the electrode material is:

[0009] ;

[0010] In the formula, It is any one of the following groups:

[0011] .

[0012] Furthermore, the structural formula of the electrode material is as follows:

[0013] .

[0014] Another object of the present invention is to provide a method for preparing the above-mentioned electrode material based on conjugated macrocyclic polymers, which includes the following steps:

[0015] A columnar aromatic derivative modified with trifluoromethanesulfonic acid, potassium carbonate, palladium dichloride of bis(triphenylphosphine)phosphine, and 4-formylphenylboronic acid were reacted in a mixed solvent of tetrahydrofuran and deionized water to obtain a columnar aromatic derivative containing an acyl group.

[0016] An acyl-containing columnar aromatic derivative and an N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine ligand are placed in a mixed solvent of o-dichlorobenzene and n-butanol, and acetic acid is added as a catalyst to carry out a Schiff base reaction to obtain the electrode material.

[0017] Furthermore, the method for synthesizing the trifluoromethanesulfonic acid-modified columnar aromatic derivative includes the following steps:

[0018] Paraformaldehyde or its derivatives and 1,4-dimethoxybenzene were dissolved in an organic solvent, and then boron trifluoride diethyl ether was added to react and give compound 1.

[0019] Compound 1 was dissolved in an organic solvent, and an aqueous solution of cerium ammonium nitrate was added dropwise to react and give compound 2.

[0020] Compound 2 was dissolved in an organic solvent and reacted with an aqueous solution of sodium dithionite to obtain compound 3.

[0021] Compound 3 was mixed with dry pyridine and an organic solvent, and trifluoromethanesulfonic acid anhydride was added dropwise to react and obtain the trifluoromethanesulfonic acid-modified columnar aromatic derivative.

[0022] Furthermore, the organic solvent is dichloromethane.

[0023] Another object of the present invention is to provide an application of the above-mentioned electrode material based on conjugated macrocyclic polymer in a zinc-ion aqueous battery.

[0024] Another object of the present invention is to provide a positive electrode using the above-mentioned electrode material based on conjugated macrocyclic polymer as the active component, wherein the electrode material improves the specific capacitance and cycle stability of the battery through Faraday and non-Faraday dual-state energy storage modes.

[0025] Furthermore, the method for preparing the positive electrode includes the following steps:

[0026] The electrode material, conductive agent, and binder are mixed to form a slurry;

[0027] The slurry is coated onto the surface of nickel foam and then dried to obtain the positive electrode.

[0028] Another object of the present invention is to provide a zinc-ion aqueous battery, comprising a negative electrode, a separator, an electrolyte, and the aforementioned positive electrode.

[0029] This invention provides an electrode material based on a conjugated macrocyclic polymer, which can be used in the field of organic zinc-ion aqueous batteries to significantly improve the specific capacitance and cycle stability of the battery. This electrode material overcomes the performance limitations of traditional electrode materials through the synergistic effect of Faraday and non-Faraday dual-state energy storage modes, providing higher energy storage efficiency and longer lifespan. This electrode material not only improves the rate performance of the battery at different current densities but also effectively extends the cycle life of the battery, exhibiting excellent electrochemical performance and stability. Compared with traditional electrode materials, batteries made using the electrode material of this invention have higher specific capacity and lower energy loss, demonstrating broad application potential. It is particularly suitable for the research and development and manufacturing of high-specific-capacity, long-life batteries, providing an efficient, economical, and sustainable battery solution suitable for new energy storage, portable devices, and electric vehicles. Attached Figure Description

[0030] Figure 1 A synthetic route diagram for electrode materials based on conjugated macrocyclic polymers provided in embodiments of the present invention.

[0031] Figure 2 This is a synthetic route diagram for the trifluoromethanesulfonic acid-modified columnar aromatic derivatives provided in an embodiment of the present invention.

[0032] Figure 3 A synthetic route diagram for columnar aromatic derivatives containing acyl groups provided in embodiments of the present invention.

[0033] Figure 4 Synthesis route diagram of electrode material P5(CHO)2-TPBD provided in embodiments of the present invention.

[0034] Figure 5 Fourier transform infrared spectra of P5(CHO)2, TPBD, and P5(CHO)2-TPBD.

[0035] Figure 6 This is a schematic diagram of the assembly of a P5(CHO)2-TPBD zinc-ion aqueous battery.

[0036] Figure 7 The energy storage mechanism of P5(CHO)2-TPBD zinc-ion aqueous battery.

[0037] Figure 8 This is a physical image of a P5(CHO)2-TPBD zinc-ion aqueous battery.

[0038] Figure 9 The GCD curve of the P5(CHO)2-TPBD zinc-ion aqueous battery is shown.

[0039] Figure 10 The graph shows the rate performance and coulombic efficiency test results of the P5(CHO)2-TPBD zinc-ion aqueous battery.

[0040] Figure 11 The graph shows the cycle stability and coulombic efficiency test results of the P5(CHO)2-TPBD zinc-ion aqueous battery. Detailed Implementation

[0041] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0042] In order to overcome the bottlenecks of the existing technology, the present invention aims to provide an electrode material based on conjugated macrocyclic polymers, which is actually an organic zinc ion aqueous battery cathode material, and solves the shortcomings of existing organic zinc ion battery cathode materials in terms of specific capacitance.

[0043] Specifically, in one embodiment of the present invention, an electrode material based on a conjugated macrocyclic polymer is provided, which is a conjugated macrocyclic polymer formed by the condensation polymerization of an acyl-containing columnar aromatic derivative and an N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine (TPBD) ligand via a Schiff base reaction.

[0044] Preferably, the general structural formula of the electrode material is:

[0045] ;

[0046] In the formula, It is any one of the following groups:

[0047] .

[0048] Preferably, the electrode material has the following structural formula:

[0049] .

[0050] In this invention embodiment, a high specific capacitance, good stability, and low cost organic zinc-ion aqueous battery cathode material was developed. This electrode material contains Faraday active sites that can participate in the redox reaction of zinc ions, providing a certain Faraday capacitance. Simultaneously, the electrode material attracts more zinc ions through the negative charge of the aromatic cavities in the polymer pillars, thereby significantly improving the battery's specific capacitance and enhancing its capacity through non-Faraday electrostatic adsorption. This invention embodiment employs a dual-state ion storage mode, combining Faraday and non-Faraday mechanisms to optimize the storage and release process of zinc ions, further improving the overall battery performance. The electrode material provided by this invention embodiment exhibits excellent electrochemical performance and is particularly suitable for applications as a high specific capacity organic zinc-ion aqueous battery cathode material.

[0051] like Figure 1 As shown, in another embodiment of the present invention, a method for preparing the above-mentioned electrode material based on conjugated macrocyclic polymer is also provided, which includes the following steps:

[0052] S1. Paraformaldehyde or its derivatives and 1,4-dimethoxybenzene are dissolved in an organic solvent, and then boron trifluoride diethyl ether is added to react and give compound 1; the molar ratio of paraformaldehyde or its derivatives, 1,4-dimethoxybenzene and boron trifluoride diethyl ether is 75:(24-26):(27-29);

[0053] S2. Compound 1 is dissolved in an organic solvent, and an aqueous solution of cerium ammonium nitrate is added dropwise to react and obtain compound 2; the molar ratio of compound 1 to cerium ammonium nitrate is 5.3:(10-12);

[0054] S3. Compound 2 is dissolved in an organic solvent and an aqueous solution of sodium dithionite is added to react and compound 3 is obtained; the molar ratio of compound 2 to sodium dithionite is 4.2:(40-42);

[0055] S4. Compound 3 is mixed with dry pyridine and an organic solvent, and trifluoromethanesulfonyl anhydride is added dropwise to react and obtain the trifluoromethanesulfonic acid-modified columnar aromatic derivative; the volume ratio of trifluoromethanesulfonyl anhydride to pyridine is (1.5-2.5):1; the molar volume ratio of compound 3 to pyridine is (0.6-0.8) mmol:1mL;

[0056] S5. A columnar aromatic derivative modified with trifluoromethanesulfonic acid, potassium carbonate, palladium dichloride of bis(triphenylphosphine) chloride, and 4-formylphenylboronic acid were reacted in a mixed solvent of tetrahydrofuran and deionized water to obtain a columnar aromatic derivative containing an acyl group; the molar ratio of the columnar aromatic derivative modified with trifluoromethanesulfonic acid to 4-formylphenylboronic acid was 1.5:(3-4); the mass ratio of the columnar aromatic derivative modified with trifluoromethanesulfonic acid, potassium carbonate, and palladium dichloride of bis(triphenylphosphine) chloride was 1.48:(1.5-2.5):(0.1-0.3).

[0057] S6. The acyl-containing columnar aromatic derivative and N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine ligand are placed in a mixed solvent of o-dichlorobenzene and n-butanol, and acetic acid is added as a catalyst to carry out a Schiff base reaction to obtain the electrode material; the molar ratio of the acyl-containing columnar aromatic derivative to the N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine ligand is 2:(0.8-1.2).

[0058] Preferably, the organic solvent is dichloromethane.

[0059] In another embodiment of the present invention, a zinc-ion aqueous battery is also provided, comprising a negative electrode, a separator, an electrolyte, and a positive electrode; wherein the preparation method of the positive electrode includes the following steps: mixing the above-mentioned electrode material (active ingredient), multi-walled carbon nanotubes (conductive agent), and polytetrafluoroethylene (binder) to form a slurry; coating the slurry onto the surface of nickel foam and drying it to obtain the positive electrode. This positive electrode combines the functionality of conjugated macrocyclic polymers, the conductivity of multi-walled carbon nanotubes, and the adhesiveness of polytetrafluoroethylene, providing an ideal positive electrode material basis for organic zinc-ion aqueous batteries.

[0060] Example 1: As Figures 2-4 As shown, this embodiment provides an electrode material based on a conjugated macrocyclic polymer, the preparation method of which includes the following steps:

[0061] Synthesis of S1 and Compound 1: 2.25 g (75.0 mmol) of paraformaldehyde and 3.5 g (25.4 mmol) of 1,4-dimethoxybenzene were dissolved in 250.0 mL of dichloromethane. Then, 3.5 mL (27.8 mmol) of boron trifluoride diethyl ether was added to the solution, and the mixture was stirred in an ice bath for 40 minutes. During this process, the color of the solution changed from white to dark green. The reaction was quenched by adding 250.0 mL of saturated sodium bicarbonate aqueous solution, causing the solution color to change from dark green to yellowish-white. After extraction and separation with dichloromethane, the crude product was separated by silica gel column chromatography. After vacuum distillation, 1.9 g of a white solid (yield: 50%), which was Compound 1, was finally obtained.

[0062] Synthesis of S2 and Compound 2: 4.0 g (5.3 mmol) of Compound 1 was dissolved in 250.0 mL of dichloromethane and placed in a 250 mL round-bottom flask. 6.0 g (10.9 mmol) of cerium ammonium nitrate was dissolved in 20.0 mL of deionized water and placed in a 100 mL constant-pressure titration funnel. The aqueous solution of cerium ammonium nitrate was added dropwise to the solution in the round-bottom flask at room temperature, and the mixture was stirred for 40 minutes. The solution gradually changed from colorless to deep red, eventually yielding a deep red liquid. After vacuum distillation, 2.0 g of a deep red solid (yield: 52%) was obtained, which was purified by silica gel column chromatography to obtain Compound 2.

[0063] Synthesis of S3 and Compound 3: 3.0 g (4.2 mmol) of Compound 2 was dissolved in 84.0 mL of dichloromethane and placed in a 250 mL round-bottom flask. 7.2 g (41.4 mmol) of sodium dithionite was dissolved in 36.0 mL of deionized water and added to the round-bottom flask. Under nitrogen protection, the mixture was stirred at room temperature for 2 hours, during which the color of the solution changed from dark red to white. After vacuum distillation, 2.8 g of a white solid (yield: 93%) was obtained, which is Compound 3. Compound 3 requires no further processing and can be used directly in subsequent steps.

[0064] Synthesis of S4, a column-modified aromatic hydrocarbon (i.e., compound 4) with trifluoromethanesulfonic acid unilateral modification [5]: 2 mL of trifluoromethanesulfonic acid anhydride was added dropwise to a mixture of 0.69 mmol of compound 3 and 1 mL of dry pyridine, using 20 mL of dry dichloromethane as the solvent, and the reaction mixture was cooled to 0 °C. Then, the reaction was stirred at room temperature for 12 hours. After the reaction was completed, the solvent was removed by vacuum concentration and separated by silica gel column chromatography, finally yielding a white powder (520 mg, yield: 76%), which is compound 4.

[0065] S5. Synthesis of the acyl-containing columnar aromatic derivative P5(CHO)2: 1.48 g (1.5 mmol) of compound 4 was placed in a 75 mL pressure-resistant flask. Under nitrogen protection, 2 g of potassium carbonate, 200 mg of bis(triphenylphosphine)-palladium dichloride, 0.53 g of 4-formylphenylboronic acid (3.5 mmol), 40 mL of tetrahydrofuran, and 10 mL of deionized water were added sequentially. The mixture was heated to reflux under sealed conditions and stirred for 72 hours. After the reaction was complete, it was cooled to room temperature, and the organic phase was separated by vacuum filtration. The crude product was then obtained by vacuum distillation, and finally purified by column chromatography to obtain the target product P5(CHO)2.

[0066] S6. The preparation method of electrode material P5(CHO)2-TPBD is as follows: P5(CHO)2 (53.94 mg, 0.06 mmol) and TPBD (14.17 mg, 0.03 mmol) were added to a mixed solvent of 0.5 mL o-dichlorobenzene and 0.5 mL n-butanol. Then, 0.2 mL of 6 M acetic acid aqueous solution was added as a catalyst to promote the Schiff base reaction. The reaction system was degassed three times to remove air from the solvent and avoid interference from oxygen in the reaction. The operation was carried out under nitrogen protection to maintain an inert environment. Subsequently, the reaction mixture was placed in an oven at 120 °C for 72 hours. After the reaction was completed, it was cooled to room temperature and washed three times with acetone and tetrahydrofuran, respectively, to obtain a yellow product, which is the electrode material P5(CHO)2-TPBD.

[0067] The Fourier transform infrared spectra of P5(CHO)2, TPBD, and P5(CHO)2-TPBD are as follows: Figure 5 As shown, this demonstrates the successful preparation of conjugated macrocyclic polymers.

[0068] It should be noted that the CAS number for TPBD ligand is 3283-07-6; the CAS number for paraformaldehyde is 30525-89-4; the CAS number for 1,4-dimethoxybenzene is 150-78-7; the CAS number for boron trifluoride ether is 109-63-7; the CAS number for cerium ammonium nitrate is 16774-21-3; and the CAS number for sodium sulfite is 7775-14-6.

[0069] Example 2: This example provides a P5(CHO)2-TPBD electrode for zinc-ion aqueous batteries, the preparation method of which includes the following steps:

[0070] First, the P5(CHO)2-TPBD polymer (as the active material), multi-walled carbon nanotubes (as the conductive agent), and polytetrafluoroethylene (as the binder) prepared in Example 1 were weighed at a mass ratio of 6:3:1. Then, these three components were thoroughly mixed in ethanol solvent to ensure uniform dispersion and the formation of a homogeneous slurry. Next, the slurry was uniformly coated onto the surface of nickel foam using a pressing process to form an electrode sheet. After coating and pressing, the electrode sheet was placed in an oven for drying. The drying conditions were 80 °C for 8 hours to remove the solvent and ensure the electrode sheet's drying stability, thus obtaining the P5(CHO)2-TPBD electrode.

[0071] Example 3: As Figure 6 As shown, this embodiment provides a zinc-ion aqueous battery, the assembly process of which includes the following steps:

[0072] First, the P5(CHO)2-TPBD electrode prepared in Example 2 above was used as the positive electrode, the Zn sheet as the negative electrode, and the NKK-MPF30AC-100 aqueous separator as the intermediate separator. Following the standard battery assembly process, the P5(CHO)2-TPBD electrode and the Zn sheet were first fixed to the positive and negative electrode positions of the battery, respectively. To ensure the stability of the battery assembly and effective electrolyte isolation, the NKK-MPF30AC-100 aqueous separator was precisely placed between the positive and negative electrodes to avoid short circuits. Then, a 2M Zn(OTf)2 aqueous solution was prepared as the battery electrolyte. 130 µL of electrolyte was uniformly injected into the battery assembly, ensuring that the electrolyte fully penetrated and filled all electrode areas of the battery, guaranteeing efficient zinc ion conduction and good battery performance. After the electrolyte injection was completed, the battery was packaged using a battery packaging machine to obtain the P5(CHO)2-TPBD zinc ion aqueous battery (button cell), as shown in the figure below. Figure 8 As shown, the packaging machine seals the battery under precise control, ensuring good sealing and preventing electrolyte leakage. Through this assembly process, an organic zinc-ion aqueous battery with excellent electrochemical performance is finally obtained, meeting the requirements for high specific capacity and stability.

[0073] The energy storage mechanism of the above-mentioned P5(CHO)2-TPBD zinc-ion aqueous battery is as follows: Figure 7As shown, the energy storage performance primarily relies on the synergistic effect of the Faraday and non-Faraday dual-state energy storage modes of the electrode material P5(CHO)2-TPBD. The electrochemical properties of P5(CHO)2-TPBD stem from its unique columnar aromatic hydrocarbon structure. Due to their strong electronegativity, columnar aromatic hydrocarbon molecules can adsorb zinc ions during battery charging and discharging. This non-Faraday effect provides additional energy storage through electrostatic adsorption, significantly enhancing the battery's specific capacitance. In this material, zinc ions are stored and released not only through Faraday redox reactions but also through non-Faraday energy storage via the electrostatic interaction of the columnar aromatic hydrocarbon cavities. The electronegativity of the columnar aromatic hydrocarbons allows zinc ions to be adsorbed on the electrode surface through non-covalent interactions, thereby improving the overall specific capacitance.

[0074] Zinc-ion aqueous battery performance testing: Comprehensive battery performance tests were conducted on the assembled P5(CHO)2-TPBD zinc-ion aqueous battery, including GCD energy storage testing, rate performance testing, and cycle stability testing. First, the GCD energy storage test was performed using different current densities (0.1, 0.5, 1, 2, 3, 4, 5, 8, 15 A·g). -1 The battery was subjected to charge-discharge cycles at various current densities, and key parameters such as charge-discharge time, specific capacity, and energy density were recorded to evaluate its energy storage capacity at different rates. The results are as follows: Figure 9 As shown; at 0.1 A g -1 At a current density of 85 mAh·g, the specific capacitance of the P5(CHO)2-TPBD zinc-ion aqueous battery is 85 mAh·g. -1 Based on Faraday theory specific capacitance calculations, the theoretical specific capacitance of the P5(CHO)2-TPBD zinc-ion aqueous battery is 27.2 mAh·g. -1 The actual specific capacitance tested was as high as 85 mAh·g. -1 This indicates that the introduction of columnar aromatics improves the utilization rate of Faraday active sites in the entire polymer backbone, and at the same time provides non-Faraday capacitance through electrostatic adsorption.

[0075] Next, rate performance testing was conducted, and the battery's charge / discharge efficiency was evaluated by calculating coulombic efficiency. Coulombic efficiency is determined by the ratio of discharge capacity to charge capacity, reflecting the energy loss during the charge / discharge process. The tested current density range also included 0.1, 0.5, 1, 2, 3, 4, 5, 8, and 15 A·g. -1 To comprehensively evaluate the battery's performance and energy efficiency at high rates, the results are as follows: Figure 10 As shown.

[0076] Finally, proceed with 2 A·g -1Cyclic stability testing involves subjecting the battery to prolonged charge-discharge cycles to assess its ability to maintain stable performance over extended periods of use. The number of cycles and the rate of capacity decay are recorded to evaluate the battery's long-term stability and durability. Results are as follows: Figure 11 As shown in the figure. These three tests comprehensively evaluate the energy storage performance, rate performance, coulombic efficiency, and cycle stability of the P5(CHO)2-TPBD zinc-ion aqueous battery, providing sufficient data support for its reliability and performance in practical applications.

[0077] Experimental results show that the electrode material provided in this invention exhibits a specific capacitance exceeding the theoretical Faraday capacitance in practical applications, indicating an additional energy storage contribution from non-Faraday interactions within the battery. Specifically, the battery's energy storage mechanism relies on both Faraday and non-Faraday modes: zinc ions participate in electron transfer and redox reactions via Faraday reactions, while non-Faraday energy storage occurs through electrostatic adsorption within the columnar aromatic cavities. This dual-state energy storage mode significantly improves the specific capacitance and stability of the battery material of this invention.

[0078] In summary, the electrode material provided in this invention significantly improves the specific capacitance and cycle stability of the battery by introducing a conjugated macrocyclic polymer with Faraday active sites, combined with both Faraday and non-Faraday dual-state ion storage mechanisms, thus meeting the requirements of high-performance batteries. Simultaneously, the electrode material, through its columnar aromatic cavity design, exhibits strong electronegativity, enabling effective adsorption of zinc ions via electrostatic adsorption, providing additional energy storage capacity and thereby enhancing the battery's capacity and stability, overcoming the limitations of traditional Faraday reactions. Furthermore, this electrode material demonstrates excellent electrochemical performance in organic zinc-ion aqueous batteries, exhibiting high specific capacity and long cycle life, making it suitable for high-efficiency battery applications. Moreover, the preparation process of the electrode material provided in this invention is relatively simple, reducing production costs and possessing broad industrial application prospects.

[0079] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification.

Claims

1. A positive electrode using an electrode material based on a conjugated macrocyclic polymer as the active component, applied to a zinc-ion aqueous battery, characterized in that, The electrode material enhances the specific capacitance and cycle stability of the battery through Faraday and non-Faraday dual-state energy storage modes; the electrode material is a conjugated macrocyclic polymer formed by the condensation polymerization of an acyl-containing columnar aromatic derivative and an N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine ligand via a Schiff base reaction; the structural formula of the electrode material is: 。 2. The positive electrode according to claim 1, characterized in that, The preparation method of the electrode material includes the following steps: A columnar aromatic derivative modified with trifluoromethanesulfonic acid, potassium carbonate, palladium dichloride of bis(triphenylphosphine)phosphine, and 4-formylphenylboronic acid were reacted in a mixed solvent of tetrahydrofuran and deionized water to obtain a columnar aromatic derivative containing an acyl group. An acyl-containing columnar aromatic derivative and an N,N,N',N'-tetra(p-aminophenyl)p-phenylenediamine ligand are placed in a mixed solvent of o-dichlorobenzene and n-butanol, and acetic acid is added as a catalyst to carry out a Schiff base reaction to obtain the electrode material.

3. The positive electrode according to claim 2, characterized in that, The method for synthesizing the trifluoromethanesulfonic acid-modified columnar aromatic derivative includes the following steps: Paraformaldehyde or its derivatives and 1,4-dimethoxybenzene were dissolved in an organic solvent, and then boron trifluoride diethyl ether was added to react and give compound 1. Compound 1 was dissolved in an organic solvent, and an aqueous solution of cerium ammonium nitrate was added dropwise to react and give compound 2. Compound 2 was dissolved in an organic solvent and reacted with an aqueous solution of sodium dithionite to obtain compound 3. Compound 3 was mixed with dry pyridine and an organic solvent, and trifluoromethanesulfonic acid anhydride was added dropwise to react and obtain the trifluoromethanesulfonic acid-modified columnar aromatic derivative.

4. The positive electrode according to claim 3, characterized in that, The organic solvent is dichloromethane.

5. The positive electrode according to claim 1, characterized in that, The method for preparing the positive electrode includes the following steps: The electrode material, conductive agent, and binder are mixed to form a slurry; The slurry is coated onto the surface of nickel foam and then dried to obtain the positive electrode.

6. A zinc-ion aqueous battery, comprising a negative electrode, a separator, and an electrolyte, characterized in that, It also includes the positive electrode as described in any one of claims 1-5.

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