High-stability pyrene tetraketone quinone polymer negative electrode material and preparation method and application thereof

Abstract

The invention discloses a high-stability pyrene tetraketone quinone polymer negative electrode material as well as a preparation method and application thereof. The negative electrode material is prepared by taking pyrene-4, 5, 9, 10-tetraone and an aminoquinone compound as reaction monomers through condensation reaction in a solvent medium, and a stable polymer structure with an expanded pi conjugated skeleton and rich proton storage active sites can be formed; the material effectively improves proton storage capacity, charge transfer dynamic performance and structural stability in a long-term cycle process, shows outstanding electrochemical performance after being assembled into an organic water-based proton battery, effectively solves the defects that a traditional organic electrode material is easy to dissolve in a water-based system, limited in specific capacity and short in cycle life, and has a wide application prospect. The method has a good application prospect in the field of energy conversion such as large-scale electrochemical energy storage.

Description

Technical Field

[0001] This invention relates to a polymer anode material, particularly to a highly stable pyrene-tetraketonoquinone polymer anode material, and also to a method for preparing the above-mentioned anode material and its application. Background Technology

[0002] The growing contradiction between environmental problems and energy shortages has made the development of large-scale energy storage devices a core prerequisite for the conversion of renewable energy into stable electricity. Aqueous rechargeable batteries, especially aqueous lithium-ion batteries (ALIBs), have become a key focus in the energy storage field due to their inherent safety, environmental compatibility, and cost-effectiveness. However, the scarcity of lithium metal resources and their continuously rising costs significantly restrict the large-scale application of ALIBs in grid-scale energy storage scenarios. Therefore, the industry has begun exploring Na... + K + Zn 2+ Mg 2+ Alternative charge carriers for use in aqueous rechargeable batteries; hydrated hydrogen ions (H3O) + ), NH4 + Although non-metallic ions have been studied due to their abundant reserves, their overall performance is usually difficult to match that of lithium-based systems due to their large ionic radius and low charge radius ratio.

[0003] In recent years, with protons (H) + Organic aqueous proton batteries, using protons as charge carriers, have emerged as highly promising energy storage technology candidates due to the small size and light weight of protons. These batteries achieve rapid proton conduction in the aqueous electrolyte through the Grotthuss mechanism, exhibiting excellent rate performance. However, inorganic materials such as MnO2, V2O5, Prussian blue analogues (PBAs), MoO3, and titanium-based oxides, although proven to possess the properties of H3O in acidic electrolytes, have shown limited performance. + Storage capacity, but generally suffers from poor structural stability, H + The ease with which materials dissolve during the intercalation-extraction process, coupled with the toxicity issues of some materials, severely limits their practical application. Organic materials, as a sustainable alternative, possess significant advantages such as structural tunability, environmental friendliness, and abundant resources. Recent studies have shown that organic compounds such as 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), pyrrolizine (ALO), and polyimides (PIs) exhibit reversible H3O... + It has some potential in terms of storage; however, existing organic H + The main materials (such as quinones and conjugated polymers) still face many technical bottlenecks: the specific capacity is relatively low (<150 mAh g). -1The low operating voltage (<0.8 V) and the easy dissolution of molecules lead to insufficient cycle stability (capacity retention rate <70% after 500 cycles). These problems seriously hinder the industrialization of organic materials in the field of energy storage batteries. In particular, conjugated polymers (such as linear or network polymers based on benzoquinone, naphthoquinone and other units), which are an important branch of organic electrode materials, have improved electronic conductivity through conjugated structures and used carbonyl groups (C=O) for proton storage. However, due to their molecular structure design, they have not effectively solved the above-mentioned bottlenecks: (1) Density and capacity limitation of active sites: Many conjugated polymers have large repeating unit structures, but the number of effective electrochemical active sites contributed by each unit is limited, which makes it difficult for their specific capacity to break through the conventional upper limit; (2) Structural instability and dissolution problems: Some existing linear conjugated polymer chains are not rigid enough or the intermolecular forces are weak. During long-term charging and discharging, especially in acidic aqueous electrolytes, chain breakage or dissolution of active components is likely to occur, resulting in rapid capacity decay; (3) Poor kinetic performance: Due to the limited expansion of the conjugated system or the unsatisfactory distribution of active sites, the resistance to the transport of electrons and ions in the bulk phase of the material is large, which limits its performance at high rates. Therefore, developing a novel conjugated polymer that can achieve high density and synergistic active sites, a highly extended and stable π-conjugated system, and a rigid structure that inhibits dissolution is the key to fundamentally improving the performance of organic aqueous proton batteries. Summary of the Invention

[0004] Purpose of the invention: The purpose of this invention is to provide a highly stable pyrene-tetraketonylquinone polymer anode material, as well as a method for preparing the above-mentioned anode material and its application in organic aqueous proton batteries.

[0005] Technical solution: The high-stability pyrene-tetraketonoquinone polymer anode material of the present invention is characterized in that the structure of the anode material is as shown in Formula I:

[0006]

[0007] Where n is a positive integer.

[0008] The preparation method of the above-mentioned highly stable pyrene-tetraketonoquinone polymer anode material includes the following steps:

[0009] (1) Mix the first monomer pyrene-4,5,9,10-tetraone with the second monomer aminoquinone to obtain a mixed monomer, add a reaction medium, wherein the reaction medium is one or a mixture of ethanol or glacial acetic acid, and stir until the mixture is evenly dispersed to obtain a mixed system;

[0010] (2) The mixture was placed in an oil bath environment for reflux reaction. After the reaction was completed, it was cooled to room temperature. The reaction product was filtered, washed and dried to obtain the high-stability pyrene-tetraketon quinone polymer anode material.

[0011] In step (1), the aminoquinone compound is selected from at least one of 2,3,5,6-tetraamino-p-benzoquinone, 2,3-diamino-1,4-naphthoquinone, 2-amino-3-chloro-1,4-naphthoquinone, or 1,4-diaminoanthraquinone, preferably 2,3,5,6-tetraamino-p-benzoquinone; the molar ratio of the first monomer to the second monomer is 1:1, the volume ratio of ethanol to glacial acetic acid in the reaction medium is 1:1, and the reaction medium is preferably glacial acetic acid.

[0012] In step (2), the reflux reaction temperature is 80~120℃ and the time is 4~24 h, preferably 110℃ and 12h; the washing is carried out in sequence with glacial acetic acid, deionized water and ethanol; the drying temperature is 60-80℃.

[0013] The aforementioned highly stable pyrene-tetraketonoquinone polymer anode material can be used in organic aqueous proton batteries.

[0014] The method for preparing the negative electrode of the organic aqueous proton battery is as follows: a high-stability pyrene-tetraketonoquinone polymer negative electrode material, conductive carbon black, and binder are mixed and dispersed in an organic solvent to obtain a slurry. The slurry is then coated onto a conductive current collector and dried to obtain the negative electrode of the organic aqueous proton battery.

[0015] The conductive current collector is one of carbon paper, titanium mesh, carbon cloth, or nickel foam; the organic solvent is N-methylpyrrolidone; the binder is polyvinylidene fluoride; the weight ratio of the high-stability pyrene-tetraketone quinone polymer negative electrode material, conductive carbon black, and binder is 6~8:1~3:1, preferably 6:3:1; the amount of organic solvent used is 1-2 times the total weight of the above three components.

[0016] Invention Principle: The high-stability pyrene-tetraketone quinone polymer anode material of this invention uses pyrene-4,5,9,10-tetraketone (pyrene-tetraketone) and aminoquinone compounds as comonomers. A long-chain symmetrical conjugated polymer structure is constructed through directional polycondensation, resulting in a regular symmetrical molecular chain. The alternating connection of naphthalene and quinone rings forms a π-conjugated system extending throughout the entire molecule. Furthermore, the polymer backbone uniformly distributes two types of active sites: C=O carbonyl groups and C=N imine bonds, constituting a dual proton storage center. The continuous electron delocalization pathway formed by the long-chain polymer structure enables synergistic proton adsorption-desorption reactions at both types of active sites, significantly increasing the total reversible proton storage. Simultaneously, the continuity of the conjugated system enhances electron transport efficiency, effectively addressing the insufficient charge transport kinetics performance of traditional organic electrode materials.

[0017] The pyrene-tetraketonylquinone polymer of this invention has a long-chain symmetrical conjugated polymer structure. Its rigid and symmetrical long-chain backbone can alleviate the local volumetric stress generated during proton insertion / extraction through segmental synergistic buffering, preventing material particle fragmentation. Simultaneously, the cross-linked network formed between long-chain molecules, combined with the interfacial interactions of C=O and C=N groups, can effectively inhibit the dissolution of active components into the electrolyte, ensuring that the polymer structure does not experience chain breakage or dissolution loss during long-term cycling. The structural integrity retention capability of this long-chain symmetrical polymer is significantly better than that of traditional organic electrode materials, resulting in a substantial improvement in the cycle stability of the assembled organic aqueous proton battery. Its cycle life and capacity retention are both superior to existing organic proton battery systems.

[0018] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The high-stability pyrene-tetraketoquinone polymer anode material of the present invention has significantly optimized proton storage capacity and charge transport rate compared with traditional organic small molecule materials, short-chain oligomers and similar materials with asymmetric structures, providing a structural basis for improving the electrochemical performance of organic aqueous proton batteries; (2) The preparation method of the anode material is simple, mild, and does not require complex catalysts or inert gas protection. The solvent used can be recycled, the reaction yield is high, and the reproducibility is good, making it suitable for industrial scale-up production; (3) An organic aqueous proton battery is assembled using the stable pyrene-tetraketoquinone polymer of the present invention as the anode and low-cost and readily available MnO2 (deposited on graphite felt) as the cathode, which has a wide voltage window and a high open-circuit voltage, and its proton storage specific capacity can reach 186.4 mAh g. -1 The full battery can reach 5 A g -1 It can stably cycle for more than 10,000 cycles at a current density, and its overall performance is significantly better than most existing organic aqueous proton battery systems. Attached Figure Description

[0019] Figure 1 This is a structural diagram of the highly stable pyrene-tetraketonoquinone polymer anode material prepared in Example 1 of the present invention;

[0020] Figure 2 This is a scanning electron microscope (SEM) schematic diagram of the highly stable pyrene-tetraketonoquinone polymer anode material prepared in Example 1 of the present invention.

[0021] Figure 3 Infrared spectra of the highly stable pyrene-tetraketonoquinone polymer anode material (PTAQ) prepared in Example 1 of this invention, and two monomers, pyrene-4,5,9,10-tetraketon (PTO) and 2,3,5,6-tetraaminop-benzoquinone (TABQ).

[0022] Figure 4The three-electrode (counter electrode - carbon rod; reference electrode - Ag / AgCl) constant current charge-discharge curves of the electrode sheet assembled from the high-stability pyrene-tetraketonoquinone polymer negative electrode material in Example 1 of this invention are shown.

[0023] Figure 5 Cyclic voltammetry curves (scan rate 0.5 mV s⁻¹) of the positive and negative electrodes of an organic aqueous proton battery assembled from the high-stability pyrene-tetraketonoquinone polymer negative electrode material prepared in Example 1 of this invention.

[0024] Figure 6 The cyclic voltammetry curves of an organic aqueous proton battery assembled from electrode sheets prepared using the high-stability pyrene-tetraketonoquinone polymer anode material in Example 1 of this invention are shown at different scan rates.

[0025] Figure 7 The image shows the long-cycle charge-discharge performance and coulombic efficiency curve of the organic aqueous proton battery assembled from the electrode sheet prepared by the high-stability pyrene-tetraketonoquinone polymer anode material in Example 1 of this invention.

[0026] Figure 8 Comparison curves of charge-discharge capacity and cycle stability of organic aqueous proton batteries after the high-stability pyrene-tetraketonoquinone polymer anode materials prepared in Examples 1-3 of this invention are shown.

[0027] Figure 9 The image shows a comparison of the three-electrode cyclic voltammetry curves (scan rate 1 mV s⁻¹) of the high-stability pyrene-tetraketonoquinone polymer anode material prepared in Example 1 of the present invention with those of the monomer material in Comparative Example 1. Detailed Implementation

[0028] The technical solution of the present invention will be further described below with reference to the embodiments. The test materials used in the embodiments can all be purchased through conventional means.

[0029] Example 1

[0030] The high-stability pyrene-tetraketonylquinone polymer anode material of the present invention is prepared by the following specific steps:

[0031] (1) Weigh 0.524 g of pyrene-4,5,9,10-tetraone and 0.336 g of 2,3,5,6-tetraaminop-benzoquinone, and grind them thoroughly in a mortar to obtain a mixed monomer; then add the mixed monomer to 100 mL of glacial acetic acid and sonicate for 30 minutes to achieve uniform dispersion of the mixed system.

[0032] (2) The mixture was placed in an oil bath and heated to 110°C, and reacted at a constant temperature for 12 hours. After the reaction was completed, it was naturally cooled to room temperature, centrifuged at 9000 rpm for 15 minutes, the precipitate was collected, and washed in the order of glacial acetic acid → ethanol → deionized water. Finally, it was dried under vacuum conditions (0.09 MPa) at 60°C for 12 hours to obtain a high-stability pyrene-tetraketonylquinone polymer anode material.

[0033] like Figure 1-3 As shown, the structure and morphology of the prepared highly stable pyrene-tetraketonylquinone polymer were verified: Figure 1 As shown, this material uses pyrene-4,5,9,10-tetraone and 2,3,5,6-tetraaminop-benzoquinone as monomers, which are polycondensed to form a long-chain conjugated structure. The main molecular chain has uniformly distributed C=O carbonyl groups and C=N imine bonds as two types of proton storage active sites, providing a structural basis for proton transport and electron conduction in electrochemical processes; Figure 2 As shown, the material exhibits a uniform granular microstructure with no obvious agglomeration. This structure can expand the contact interface between the material and the electrolyte while ensuring sufficient exposure of active sites; Figure 3 As shown, in the infrared spectrum of the polymer (PTAQ), the C=O characteristic peak of the monomer pyrene-4,5,9,10-tetraone and the -NH2 characteristic peak of 2,3,5,6-tetraaminop-benzoquinone disappeared, and a new C=N characteristic peak was added, directly proving that the monomers successfully underwent a condensation reaction.

[0034] Electrode sheets were prepared using the materials from Example 1. The obtained polymer material, conductive carbon black, and polyvinylidene fluoride binder were mixed in a weight ratio of 6:3:1. An appropriate amount of N-methylpyrrolidone was added to form a slurry, which was then uniformly coated onto the current collector. This electrode sheet serves as the working electrode for subsequent testing or as the negative electrode for assembling a full cell. Subsequently, using this electrode sheet as the working electrode, a three-electrode test system (working electrode, counter electrode - carbon rod, reference electrode - Ag / AgCl) was assembled, and performance tests were conducted (this three-electrode test system is a conventional electrochemical testing method in the art for evaluating the half-cell performance of electrode materials).

[0035] like Figure 4 As shown, in 1 Ag -1 ~10 A g -1 Within the current density range, the material exhibits a clear charge-discharge plateau, 1 A g -1 The discharge specific capacity can reach 248.6 mAh g. -1 10 A g -1 It still maintains 157.3 mAh g. -1 This demonstrates excellent rate adaptability; such as Figure 5 As shown, 0.5 mV s -1In the cyclic voltammetry (CV) curves of the positive and negative electrodes at the scan rate, the peak shapes of the reduction / oxidation peaks at the negative electrode and the oxidation / reduction peaks at the positive electrode are symmetrical, and the potential difference between the positive and negative electrodes reaches 1.43 V, proving that the proton insertion-extraction reaction is reversible; Figure 6 As shown, with scan rate (1 mV s) -1 ~10 mV s -1 The improved performance, small CV peak shift, near 1:1 peak current ratio between oxidation and reduction peaks, and peak position difference ≤50mV indicate that the proton insertion-extraction reaction of PTAQ material has excellent electrochemical reversibility. This demonstrates that the material has excellent charge transport kinetics and can respond quickly to electrochemical reactions at different rates.

[0036] Example 2

[0037] The high-stability pyrene-tetraketonoquinone polymer anode material of the present invention is prepared by adjusting the reaction medium to a 1:1 volume ratio of ethanol to glacial acetic acid, and adjusting the oil bath temperature to 100°C for 24 hours. The specific preparation steps are as follows:

[0038] (1) Weigh 0.524 g of pyrene-4,5,9,10-tetraone and 0.336 g of 2,3,5,6-tetraaminop-benzoquinone, and grind them thoroughly in a mortar to obtain a mixed monomer; then add the mixed monomer to a mixture of 100 mL of ethanol and glacial acetic acid in a volume ratio of 1:1, and sonicate for 30 minutes to achieve uniform dispersion of the mixed system;

[0039] (2) The mixture was placed in an oil bath and heated to 100°C, and reacted at a constant temperature for 24 hours. After the reaction was completed, it was naturally cooled to room temperature, centrifuged at 9000 rpm for 15 minutes, the precipitate was collected, and washed in the order of glacial acetic acid → ethanol → deionized water. Finally, it was dried at 60°C under a vacuum of 0.09 MPa for 12 hours to obtain a high-stability pyrene-tetraketonylquinone polymer anode material.

[0040] Example 3

[0041] The high-stability pyrene-tetraketonylquinone polymer anode material of the present invention is prepared by adjusting the reaction medium to ethanol, adjusting the oil bath temperature to 90°C, and holding for 6 hours. The specific preparation steps are as follows:

[0042] (1) Weigh 0.524 g of pyrene-4,5,9,10-tetraone and 0.336 g of 2,3,5,6-tetraaminop-benzoquinone, and grind them thoroughly in a mortar to obtain a mixed monomer; then add the mixed monomer to 100 mL of ethanol and sonicate for 30 minutes to achieve uniform dispersion of the mixed system.

[0043] (2) The mixture was placed in an oil bath and heated to 90°C, and reacted at a constant temperature for 6 hours. After the reaction was completed, it was naturally cooled to room temperature, centrifuged at 9000 rpm for 15 minutes, the precipitate was collected, and washed in the order of glacial acetic acid → ethanol → deionized water. Finally, it was dried under vacuum conditions (0.09 MPa) at 60°C for 12 hours to obtain a high-stability pyrene-tetraketonylquinone polymer anode material.

[0044] Comparative Example 1

[0045] An electrode sheet was prepared using the monomeric material pyrene-4,5,9,10-tetraone (PTO) as the working electrode.

[0046] 6 g of pyrene-4,5,9,10-tetraone (PTO), 3 g of acetylene black, and 1 g of polyvinylidene fluoride were weighed and dispersed in 10 g of N-methylpyrrolidone. After stirring and dispersing evenly, the mixture was uniformly coated onto carbon cloth and dried under vacuum at 60 °C to obtain an electrode sheet. Subsequently, using this electrode sheet as the working electrode, 2 M sulfuric acid solution as the electrolyte, a carbon rod as the counter electrode, and Ag / AgCl as the reference electrode, a three-electrode testing system was assembled. The test was conducted at 1 mV s. -1 Cyclic voltammetry (CV) curves were tested at scan rate.

[0047] The electrode sheets prepared with the materials from Examples 1-3 were assembled into an organic aqueous proton battery, and the full-cell performance was verified: For example... Figure 7 As shown, the battery assembled with the materials in Example 1 was tested at 5 A g. -1 After 10,000 cycles at the current density, the discharge specific capacity retention rate reached 87.5%, and the coulombic efficiency remained close to 100%, indicating that the material showed no significant dissolution of active components or structural damage during long-term cycling, demonstrating outstanding cycle stability. Figure 8 As shown, the charge-discharge capacity of Example 1 is significantly higher than that of Examples 2 and 3. This is because the reaction under glacial acetic acid medium can maximize the extension of the conjugated system, reduce intramolecular tension, ensure the orderly distribution of active sites, suppress side reactions and improve product purity, thereby giving the full battery better electrochemical performance.

[0048] In summary, the highly stable pyrene-tetraketonoquinone polymer anode material prepared by this invention achieves high specific capacity and excellent kinetic characteristics in a half-cell system through the design of a long-chain conjugated structure and dual active sites; and exhibits high rate adaptability and ultra-long cycle stability in a full-cell system. It effectively solves the technical defects of traditional organic electrode materials, such as easy solubility in aqueous systems, limited specific capacity, and short cycle life, and provides a high-performance electrode material option for the field of large-scale electrochemical energy storage.

Claims

1. A highly stable pyrene-tetraketonylquinone polymer anode material, characterized in that, The structure of the negative electrode material is shown in Formula I: ； Where n is a positive integer.

2. A method for preparing the high-stability pyrene-tetraketonoquinone polymer anode material according to claim 1, characterized in that, Includes the following steps: (1) Mix the first monomer pyrene-4,5,9,10-tetraone with the second monomer aminoquinone compound to obtain a mixed monomer, add a reaction medium, wherein the reaction medium is one or a mixture of ethanol or glacial acetic acid, and stir until evenly dispersed; (2) The mixture was placed in an oil bath environment for reflux reaction. After the reaction was completed, it was cooled to room temperature. The reaction product was filtered, washed and dried to obtain the high-stability pyrene-tetraketon quinone polymer anode material.

3. The preparation method according to claim 2, characterized in that, In step (1), the aminoquinone compound is selected from at least one of 2,3,5,6-tetraamino-p-benzoquinone, 2,3-diamino-1,4-naphthoquinone, 2-amino-3-chloro-1,4-naphthoquinone, or 1,4-diaminoanthraquinone.

4. The preparation method according to claim 2, characterized in that, In step (1), the molar ratio of the first monomer to the second monomer is 0.8~1.2:1, and the volume ratio of ethanol to glacial acetic acid in the reaction medium is 0.5~2:

1.

5. The preparation method according to claim 2, characterized in that, In step (2), the reflux reaction temperature is 80~120℃ and the time is 4~24 h.

6. The application of the highly stable pyrene-tetraketonoquinone polymer anode material according to claim 1 in an organic aqueous proton battery.

7. The application according to claim 6, characterized in that, The method for preparing the negative electrode of an organic aqueous proton battery is as follows: a high-stability pyrene-tetraketonoquinone polymer negative electrode material, conductive carbon black, and a binder are mixed and dispersed in an organic solvent to obtain a slurry. The slurry is then coated onto a conductive current collector and dried to obtain the negative electrode of the organic aqueous proton battery.

8. The application according to claim 6, characterized in that, The conductive current collector is one of carbon paper, titanium mesh, carbon cloth, or nickel foam.

9. The application according to claim 6, characterized in that, The organic solvent is N-methylpyrrolidone; the binder is polyvinylidene fluoride.

10. The application according to claim 6, characterized in that, The weight ratio of highly stable pyrene-tetraketonoquinone polymer anode material, conductive carbon black, and binder is 6~8:1~3:1.

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