Aqueous organic zinc ion battery positive pole piece, preparation method and application thereof

Abstract

The invention relates to a water-based organic zinc ion battery positive pole piece as well as a preparation method and application thereof. The water-based organic zinc ion battery positive pole piece consists of a positive organic active substance, a conductive agent, a binder and a current collector, the positive electrode organic active material is one or more of a phenothiazine aromatic heterocyclic compound containing a sulfur sulfone group, a phenoxazine aromatic heterocyclic compound containing a sulfur sulfone group and a phenoselenazine aromatic heterocyclic compound containing a sulfur sulfone group. The aqueous zinc ion battery prepared by the invention has high safety, good cycle performance under relatively large current density, high charge-discharge window, low preparation cost and environmental friendliness. In addition, the content of materials for preparing the battery is very rich in nature. The invention has a development prospect in the fields of future energy storage, 3C equipment power supplies, power equipment power supplies and the like.

Description

Technical Field

[0001] This invention relates to the field of zinc-ion battery technology, and in particular to a positive electrode sheet for an aqueous organic zinc-ion battery, its preparation method, and its application. Background Technology

[0002] Although high-energy-density lithium-ion batteries currently dominate the commercial rechargeable battery market, their further development is constrained by the limited availability of lithium resources, high costs, and safety concerns associated with organic electrolytes. Against this backdrop, aqueous zinc-ion batteries are gaining increasing attention due to their advantages, including the use of aqueous electrolytes, lower costs, environmental friendliness, and high safety. Zinc metal, as a negative electrode material, exhibits a high theoretical capacity (820 mAh / g) and a low redox potential (relative to -0.76 V for the standard hydrogen electrode), demonstrating promising application prospects. Therefore, aqueous zinc-ion batteries are considered a promising green electrochemical energy storage system, possessing advantages such as high power density, simple fabrication processes, and controllable costs.

[0003] In aqueous zinc-ion batteries, cathode materials mainly include manganese-based oxides, vanadium-based compounds, Prussian blue-based inorganic materials, and organic compounds. These materials, with their unique structures, enable reversible insertion and extraction of zinc ions, thereby storing and releasing energy. Among them, organic cathode materials have attracted attention due to their high discharge specific capacity, high operating voltage platform, structural diversity, and strong tunability. Through molecular structure design, their electrochemical performance can be effectively optimized, while also possessing the advantages of resource renewability and good environmental compatibility.

[0004] In terms of fabrication processes, organic cathode materials exhibit unique comprehensive performance advantages in aqueous zinc-ion batteries compared to traditional inorganic materials. While some inorganic materials, such as functional glasses and special ceramics, are irreplaceable in specific applications, the structural tunability and environmental friendliness of organic materials within battery systems give them greater development potential. Organic materials typically possess multiple electrochemical active centers and less inactive "dead mass," thus exhibiting higher theoretical and actual specific capacities. Although their output voltage is relatively low, their overall electrochemical performance can be effectively improved through reasonable structural design and process optimization.

[0005] Several reports have been published on the use of aromatic heterocyclic structures as cathode materials in the prior art. However, these materials still have problems such as dispersed free radical electron distribution, more side reactions, or insufficient stability of the oxidation state structure, resulting in poor cycle stability of the assembled zinc-ion batteries, especially low charge and discharge efficiency under high current density conditions.

[0006] Therefore, developing high-performance organic cathode materials will not only help meet the needs of future energy storage technology development, but also promote their widespread application in electric vehicles, large-scale energy storage, and portable electronic devices. Through continuous material innovation and process improvement, organic cathode materials are expected to become a key component of next-generation high-performance aqueous zinc-ion batteries.

[0007] In conclusion, it is necessary to propose a new technical solution to overcome the shortcomings of existing technologies and improve the cycle stability and high-rate performance of organic cathode materials in aqueous zinc-ion batteries. Summary of the Invention

[0008] This invention provides a positive electrode sheet for an aqueous organic zinc-ion battery, disclosing a method for preparing the same positive electrode sheet and the aqueous organic zinc-ion battery made therefrom. The battery uses phenothiazine aromatic heterocyclic compounds containing sulfone groups, phenotoxazine aromatic heterocyclic compounds containing sulfone groups, and phenotelenzine aromatic heterocyclic compounds containing sulfone groups as the positive electrode organic active materials, combined with conductive agents and binders, and prepared by a coating method. Specific steps include mixing, grinding, coating, drying, sphericalizing, and assembly. The aqueous zinc-ion battery prepared by this invention possesses high safety, good cycle performance at a high current density (3 A / g), a high charge-discharge window, low manufacturing cost, and environmental friendliness. Furthermore, the materials used in battery preparation are abundant in nature, especially zinc ore, with global reserves of approximately 230 million tons. This invention has promising applications in future energy storage, 3C device power supplies, and power equipment power supplies.

[0009] Therefore, it is necessary to provide a positive electrode sheet for an aqueous organic zinc-ion battery, the positive electrode sheet of which includes a current collector and a positive active layer disposed on the current collector; The positive electrode active layer includes a positive electrode organic active material, a conductive agent, and a binder; The positive electrode organic active material is selected from one or more of the following: phenazine aromatic heterocyclic compounds containing sulfone groups, phenothiazine aromatic heterocyclic compounds containing sulfone groups, phenotoxazine aromatic heterocyclic compounds containing sulfone groups, and phenotelezine aromatic heterocyclic compounds containing sulfone groups.

[0010] Specifically, high capacity retention at high current densities: The aqueous organic zinc-ion battery of this invention exhibits excellent rate performance and stable capacity retention. Experimental data shows that even at high current densities, the battery can still achieve stable charge-discharge cycles, and its capacity retention is significantly better than that of traditional material systems. Compared to traditional electrode materials, this invention can complete the charging and discharging of the target amount of energy in a shorter time, demonstrating superior high-rate charge-discharge characteristics, thereby significantly improving the battery's power output and practical application efficiency.

[0011] Furthermore, the positive electrode organic active material is selected from the following structures: ; R1 and R2 are selected from one or more of hydrogen atoms, phenazine aromatic heterocyclic compounds, phenoxazine aromatic heterocyclic compounds, phenselenidine aromatic heterocyclic compounds, and phenothiazine aromatic heterocyclic compounds; n1 is selected from 1-3; n2 is selected from 1-3; X is selected from one or more of S, N, O, and Se; R3 is selected from one or more of the following: phenazine aromatic heterocyclic compounds, phenoxazine aromatic heterocyclic compounds, phenselenidine aromatic heterocyclic compounds, and phenothiazine aromatic heterocyclic compounds.

[0012] Specifically, the positive electrode organic active material is selected from bis[4-(N-phenoxazine)phenyl]sulfone, 2-(4a,5-dihydrophenazin-5-yl)thiathracene-5,5-dioxide, 2-(10H-phenoxazin-10-yl)thiathracene-5,5-dioxide, 2-(10H-phenoxazin-10-yl)thiathracene-5,5-dioxide, 2-(10H-phenosenzazin-10-yl)thiathracene-5,5-dioxide, 1,3-bis(4a,5-dihydrophenazin-5-yl)thiathracene-5,5-dioxide, 1,3-bis(10H-phenoxazin-10-yl)thiathracene-5,5-dioxide, 1,3-bis(10H-phenoxazin-10-yl)thiathracene-5,5-dioxide, 1,3-bis(10H- ... Phenylseleno-10-yl)thiathracene-5,5-dioxide, 2,8-bis(4a,5-dihydrophenazin-5-yl)thiathracene-5,5-dioxide, 2,8-bis(10H-phenoxazin-10-yl)thiathracene-5,5-dioxide, 2,8-bis(10H-phenthiazin-10-yl)thiathracene-5,5-dioxide, 2,8-bis(10H-phenylseleno-10-yl)thiathracene-5,5-dioxide, 2-(12-(thiathracene-5,5-dioxide-2-yl)-5,12-dihydroquinoxolino[2,3-b]phenazin-5-yl)thiathracene-5,5-dioxide, 2-(14-(thiathracene-5,5-dioxide-2-yl)-7,14-dihydrobenzo[5,6][1,4] Oxazizo[2,3-b]phenoxazin-7-yl)thiathracene-5,5-dioxide, 2-(14-(thiathracene-5,5-dioxide-2-yl)-7,14-dihydrobenzo[5,6][1,4]thiazo[2,3-b]phenoxazin-7-yl)thiathracene-5,5-dioxide, 2-(14-(thiathracene-5,5-dioxide-2-yl)-7,14-dihydrobenzo[5,6][1,4]selezo[2,3-b]phenselezo-7-yl)thiathracene-5,5-dioxide, 2-(4a,5-dihydrophenoxazin-5-yl)thiathracene-5,5,10,10-tetraoxide, 2-(10H-phenoxazin-10-yl)thiathracene-5,5,10,10-tetraoxide, 2-(10 H-Phenothiazin-10-yl)thianthracene-5,5,10,10-tetraoxide, 2-(10H-phenselezin-10-yl)thianthracene-5,5,10,10-tetraoxide, 2,8-bis(4a,5-dihydrophenazin-5-yl)thianthracene-5,5,10,10-tetraoxide, 2,8-bis(10H-phenoxazin-10-yl)thianthracene-5,5,10,10-tetraoxide, 2,8-bis(10H-phenoxazin-10-yl)thianthracene-5,5,10,10-tetraoxide, 2,8-bis(10H-phenselezin-10-yl)thianthracene-5,5,10,10-tetraoxide, 2,8-bis(10H-phenselezin-10-yl)thianthracene-5,5,10,10-tetraoxide, 2-(12-(thianthracene-5,5-dioxide-2-yl)-5,12-dihydroquinoxalo[2,[3-b]phenazin-5-yl)thiazine-5,5-dioxide, 2,2'-[(7,14-dihydrobenzo[5,6][1,4]oxazin[2,3-b]phenoxazine)-7,14-diyl]bis(thiazine-5,5,10,10-tetraoxide), 2,2'-[(7,14-dihydrobenzo[5,6][1,4]thiazin[2,3-b]phenthiazine)-7,14-diyl]bis(thiazine-5,5,10,10-tetraoxide), 2,2'-[(7,14-dihydrobenzo[5,6][1,4]thiazin[2,3-b]phenthiazine)-7,14-diyl]bis(thiazine-5,5,10,10-tetraoxide), 2,2'-[(7,14-dihydrobenzo[5,6][1, 4]Selenazido[2,3-b]phenselenazide)-7,14-diyl]bis(thiaphen-5,5,10,10-tetraoxide), 5-(4-benzenesulfonylphenyl)-4a,5-dihydrophenazine, 10-(4-benzenesulfonylphenyl)-10H-phenoxazine, 10-(4-benzenesulfonylphenyl)-10H-phenthiazine, 10-(4-benzenesulfonylphenyl)-10H-phenselenazide, 10,10'-[5-benzenesulfonyl-1,3-phenylene]bis(10H-phenthiazine), 10,10'-[5-benzenesulfonyl-1,3-phenylene]bis(10H-phenthiazine), 10,10'-[5-benzenesulfonyl-1,3-phenylene]bis(10H-phenthiazine), [-phenylene]bis(10H-phenoxazine), 10,10'-[5-benzenesulfonyl-1,3-phenylene]bis(10H-phenoxazine), 5,5'-[5-benzenesulfonyl-1,3-phenylene]bis(4a,5-dihydrophenazine), 5,5'-[sulfonylbis(1,4-phenylene)]bis(4a,5-dihydrophenazine), 10,10'-[sulfonylbis(1,4-phenylene)]bis(10H-phenthiazine), 10,10'-[sulfonylbis(1,4-phenylene)]bis(10H-phenoselenazine), 5,12-bis( One or more of the following: (4-benzenesulfonylphenyl)-5,12-dihydroquinoxolino[2,3-b]phenazine, (7,14-bis(4-benzenesulfonylphenyl)-7,14-dihydrobenzo[5,6][1,4]thiazino[2,3-b]phenothiazine, (7,14-bis(4-benzenesulfonylphenyl)-7,14-dihydrobenzo[5,6][1,4]selezizino[2,3-b]phelenzozine, and (7,14-bis(4-benzenesulfonylphenyl)-7,14-dihydrobenzo[5,6][1,4]oxazino[2,3-b]phenoxazine.

[0013] Furthermore, the positive electrode organic active material is selected from the following structures: .

[0014] Preferably, the positive electrode organic active material is bis[4-(N-phenoxazine)phenyl]sulfone.

[0015] Specifically, in the positive electrode of the aqueous organic zinc-ion battery, bis[4-(N-phenoxazine)phenyl]sulfone sulfide (PXZ-DPS) is used as the positive electrode organic active material. As a fused heterocyclic compound, PXZ-DPS, due to the presence of lone pairs of electrons, has heteroatoms such as N or O considered to be the redox active part, which provides active sites in the reaction process of PXZ-DPS, exhibiting good electrochemical activity.

[0016] The bis[4-(N-phenoxazine)phenyl]sulfone sulfide (PXZ-DPS) was used as the positive electrode organic active material. As a fused heterocyclic compound, PXZ-DPS, due to the presence of lone pairs of electrons, has heteroatoms such as N or O considered to be part of the redox activity, providing active sites in the reaction process and exhibiting good electrochemical activity. Furthermore, systematic redox chemical studies showed that oxidized PXZ-DPS… •+ The free radical electrons mainly accumulate around the N and O atoms and further delocalize into the entire conjugated structure, which is beneficial to the free radical species PXZ-DPS. •+ It plays an important role in stabilizing the system, reducing the occurrence of free radical side reactions, and is not easily decomposed under high current density, resulting in good reversibility of electrochemical reactions.

[0017] Furthermore, the PXZ-DPS molecular structure exhibits centrosymmetry and even demonstrates better structural stability and enhanced aromaticity after oxidation, indicating its advantage in battery cycle stability. This allows batteries containing this zinc-ion battery cathode material to exhibit both high capacity at high current densities and high capacity retention over long cycles.

[0018] Meanwhile, during charging and discharging, the active sites (O) of PXZ-DPS can couple with zinc ions to form coordination bonds, and it has four active sites, which can provide considerable capacity at high current densities. In addition, its large benzene ring / fused ring can inhibit degradation during cycling, thereby further enhancing the cycle stability of zinc batteries and the charge and discharge efficiency at high current densities.

[0019] Based on the same design concept, a series of high-performance cathode materials can be derived to meet the specific requirements of battery energy density, power density, and cycle life in different application scenarios. For example, electronic conductivity can be improved by enhancing the planarity and conjugation of molecules, or the anchoring and reversible insertion / extraction of zinc ions can be promoted by introducing strongly polar groups. Therefore, the technical solution proposed in this invention is not limited to specific molecular structures, but provides a scalable and optimizable material platform, laying a solid foundation for the development of next-generation high-performance, customized aqueous zinc-ion batteries.

[0020] Furthermore, the conductive agent is selected from one or more of carbon black, graphene, acetylene black, or Ketjen black.

[0021] Furthermore, the adhesive is selected from one or more of PTFE (polytetrafluoroethylene) or PVDF (polyvinylidene fluoride).

[0022] Furthermore, the current collector is selected from one or more of carbon cloth, titanium mesh, or stainless steel mesh.

[0023] Furthermore, the mass ratio of the positive electrode organic active material, conductive agent, and binder is 1:(0.5-1.5):(0.1-1).

[0024] The present invention also provides a method for preparing the positive electrode sheet of the aqueous organic zinc-ion battery, comprising the following steps: S1. Mix the positive electrode organic active material, conductive agent and binder, grind them evenly to obtain a slurry; S2. The slurry is coated onto the current collector to form a positive electrode active layer, heated and dried, and then cut to obtain the positive electrode sheet of the aqueous organic zinc ion battery.

[0025] Furthermore, in step S1, the grinding time is 5-60 min.

[0026] Furthermore, in step S2, the heating temperature is 45-200℃.

[0027] Further, in step S2, the coating method is selected from one or more of wet coating, roller coating, extrusion coating or dip coating.

[0028] Further, in step S2, the coating loading ranges from 0.5 to 20 mg / cm³. 2 .

[0029] The present invention also provides an aqueous organic zinc-ion battery, which comprises, from top to bottom: a negative electrode shell, a negative electrode sheet, a separator, a positive electrode sheet, a gasket, a washer, and a positive electrode shell; The positive electrode sheet is the positive electrode sheet of the aqueous organic zinc-ion battery. An electrolyte is disposed between the positive electrode and the negative electrode, and the diaphragm is wetted by the electrolyte.

[0030] The aqueous organic zinc-ion battery of this invention provides excellent electrochemical performance without significantly increasing its overall production cost compared to traditional lithium-ion battery systems. Zinc resources are far more abundant than lithium resources, with a wide availability and stable price, providing a solid resource guarantee for the large-scale preparation of cathode materials and the sustainable application of the battery. Furthermore, this battery system uses an aqueous electrolyte, and its preparation process is simple, requiring no strict drying room for assembly in air, effectively reducing production energy consumption and environmental control costs. After achieving large-scale production, it is expected to demonstrate even more competitive cost-effectiveness.

[0031] The aqueous organic zinc-ion battery of this invention uses an environmentally friendly electrolyte, reducing environmental pollution. Compared to lithium batteries, which cause pollution from nickel, cobalt, and fluorine, as well as organic matter, dust, and acid / alkali contamination, and unlike inorganic cathode materials that rely on heavy metals (such as cobalt and nickel), the organic materials used in this invention have C, H, O, and N as their core constituent elements, fundamentally avoiding the long-term ecotoxicity of heavy metals. Furthermore, the organic materials used in this invention are all biodegradable, resulting in less environmental pollution and better recycling of discarded batteries, making it an ideal environmentally friendly battery.

[0032] Furthermore, the negative electrode sheet is a polished zinc sheet.

[0033] Furthermore, the negative electrode sheet is a 100% pure zinc sheet that has been polished with sandpaper, and the sandpaper has a mesh size of 800-2000.

[0034] Furthermore, the electrolyte is selected from one or more of zinc sulfate solution, zinc trifluoromethanesulfonate solution, or zinc chloride solution.

[0035] Furthermore, the concentration of the electrolyte is 0.5-8 M.

[0036] The aqueous organic zinc-ion battery of this invention uses an aqueous electrolyte, fundamentally solving the safety hazards of flammability and explosion associated with traditional organic electrolytes. Even under extreme conditions such as overcharging, short circuits, or mechanical abuse, this battery system still exhibits excellent structural and electrochemical stability. Compared to lithium-ion batteries, which are prone to thermal runaway, this invention effectively avoids risks such as high temperatures and combustion, significantly improving the safety and reliability of the battery during operation and storage. This characteristic makes it of great value in applications with extremely high safety requirements, such as large-scale energy storage.

[0037] Furthermore, the diaphragm is made of glass fiber.

[0038] The present invention has the following beneficial effects: This invention proposes an aqueous organic zinc-ion battery positive electrode sheet, its preparation method, and an aqueous organic zinc-ion battery made therefrom. The invention combines molecular designability, structural stability, and environmental friendliness. By flexibly controlling the heteroatom type, connection sites, and conjugated framework, the redox potential, electron conduction, and zinc ion affinity of the material can be optimized. The strongly electron-withdrawing sulfone group effectively stabilizes the oxidized intermediate and suppresses side reactions, while the rigid aromatic ring framework ensures rapid electron transport and cycle durability. Simultaneously, it is based on abundant elements (C, H, O, N, S), avoiding dependence on precious metals and aligning with the development direction of low-cost, green, and sustainable energy storage.

[0039] The nitrogen and oxygen heteroatoms on the aromatic heterocycle act as redox centers, undergoing reversible electron gain and loss, while zinc ions (Zn) in the electrolyte... 2+ It can reversibly coordinate or dissociate with it to achieve charge balance; although the sulfone group does not directly participate in the reaction, its strong electron-withdrawing effect can effectively stabilize the oxidized state (such as free radical cations), delocalize the charge to the entire conjugated skeleton, thereby suppressing side reactions, improving structural reversibility, and ultimately achieving high coulombic efficiency and long cycle life.

[0040] Based on the above design, this type of material exhibits outstanding performance, especially in high-rate, long-cycle performance. Taking the representative compound PXZ DPS as an example, after 1200 cycles at a high current density of 3A / g, the capacity retention rate reaches 100%, and the capacity decay is gradual and the coulombic efficiency remains above 99% in a wide rate range test from 0.2A / g to 20A / g, proving that it has excellent reaction reversibility and structural robustness. At the same time, the material has low solubility in aqueous electrolytes, and by combining the zinc anode with the aqueous system, it achieves a unified energy storage performance of high safety, high power, and long life. Attached Figure Description

[0041] Figure 1The molecular structure diagram of PXZ-DPS, the positive electrode organic active material of Example 1, is shown.

[0042] Figure 2 An assembly structure diagram of an aqueous organic zinc-ion battery is shown.

[0043] Figure 3 The cycling performance of the aqueous organic zinc-ion battery prepared in Application Example 1 is shown.

[0044] Figure 4 The cycling performance of the aqueous organic zinc-ion battery prepared in Application Example 2 is shown.

[0045] Figure 5 The cycling performance of the aqueous organic zinc-ion battery prepared in Application Example 3 is shown.

[0046] Figure 6 The cycling performance of the aqueous organic zinc-ion battery prepared in Comparative Application Example 1 is shown in the diagram.

[0047] Figure 7 The rate performance diagram of the aqueous organic zinc-ion battery prepared in Application Example 1 is shown.

[0048] Figure 8 The rate performance diagram of the aqueous organic zinc-ion battery prepared in Application Example 2 is shown.

[0049] In the diagram: 1. Negative electrode shell; 2. Negative electrode plate; 3. Separator; 4. Positive electrode plate; 5. Gasket; 6. Washer; 7. Positive electrode shell. Detailed Implementation

[0050] To more clearly illustrate the technical solution of the present invention, the following embodiments are provided. Unless otherwise stated, the raw materials, reactions, and post-processing methods appearing in the embodiments are all commercially available raw materials and technical methods well known to those skilled in the art.

[0051] The terms "preferred," "more preferably," and "more suitable" used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0052] It should be understood that, except in any operational instance or otherwise indicated, all figures representing the amounts of ingredients used, for example, in the specification and claims, should be understood to be modified in all cases by the term "about". Therefore, unless otherwise stated, the numerical parameters set forth in the following specification and appended claims are approximations varying with the desired performance to be obtained according to the invention.

[0053] In the example, the 15 wt% PTFE solution was obtained by mixing Dyneon PTFE TF5070GZ (3M Corporation, USA) with water.

[0054] Example 1 A positive electrode sheet for an aqueous organic zinc-ion battery, the positive electrode sheet comprising a current collector carbon cloth with a thickness of 0.5 mm and a positive electrode active layer with a thickness of 0.05 mm disposed on the carbon cloth; The positive electrode active layer is composed of the positive electrode organic active material bis[4-(N-phenoxazine)phenyl]sulfone (PXZ-DPS), the conductive agent Ketjen black, and the binder PTFE.

[0055] The preparation method of the above-mentioned aqueous organic zinc-ion battery positive electrode sheet includes the following steps: S1. PXZ-DPS, Ketjen black and 15wt% PTFE solution are mixed to obtain a mixture with a solid mass ratio of PXZ-DPS: Ketjen black: PTFE of 1:1:1. The mixture is then ground thoroughly in a mortar for 30 minutes to obtain a slurry. S2. The slurry is coated onto carbon cloth using a wet coating method to form a positive electrode active layer. The total loading of PXZ-DPS, Ketjen Black, and PTFE is 10 mg / cm³. 2 The sample was placed in a drying oven and dried at 80°C for 360 minutes. Then it was cut and diced to obtain the positive electrode sheet of the aqueous organic zinc-ion battery.

[0056] Example 2 A positive electrode sheet for an aqueous organic zinc-ion battery, the positive electrode sheet comprising a current collector carbon cloth with a thickness of 0.5 mm and a positive electrode active layer with a thickness of 0.05 mm disposed on the carbon cloth; The positive electrode active layer is composed of 5,5'-[sulfonylbis(1,4-phenylene)]bis(4a,5-dihydrophenazine), Ketjen black, a conductive agent, and PTFE, a binder.

[0057] The preparation method of the above-mentioned aqueous organic zinc-ion battery positive electrode sheet includes the following steps: S1. 5,5'-[sulfonylbis(1,4-phenylene)]bis(4a,5-dihydrophenazine), Ketjen black, and a 15 wt% PTFE solution were mixed to obtain a mixture with a solid mass ratio of 1:1:1 of 5,5'-[sulfonylbis(1,4-phenylene)]bis(4a,5-dihydrophenazine): Ketjen black:PTFE. The mixture was then ground thoroughly in a mortar for 30 min to obtain a slurry. S2. The slurry is coated onto carbon cloth using a wet coating method to form a positive electrode active layer. The total loading of 5,5'-[sulfonylbis(1,4-phenylene)]bis(4a,5-dihydrophenazine), Ketjen black, and PTFE is 10 mg / cm³. 2 The sample was placed in a drying oven and dried at 80°C for 360 minutes. Then it was cut and diced to obtain the positive electrode sheet of the aqueous organic zinc-ion battery.

[0058] Example 3 A positive electrode sheet for an aqueous organic zinc-ion battery, comprising a current collector carbon cloth with a thickness of 0.5 mm and a positive electrode active layer with a thickness of 0.05 mm disposed on the carbon cloth; the positive electrode active layer is... It consists of 10,10'-[sulfonylbis(1,4-phenylene)]bis(10H-phenthiazine), conductive agent Ketjen black, and binder PTFE.

[0059] The preparation method of the above-mentioned aqueous organic zinc-ion battery positive electrode sheet includes the following steps: S1. 10,10'-[sulfonylbis(1,4-phenylene)]bis(10H-phenothiazine), Ketjen black, and a 15 wt% PTFE solution were mixed to obtain a mixture with a solid mass ratio of 1:1:1 of 10,10'-[sulfonylbis(1,4-phenylene)]bis(10H-phenothiazine): Ketjen black:PTFE. The mixture was then ground thoroughly in a mortar for 30 min to obtain a slurry. S2. The slurry is coated onto carbon cloth using a wet coating method to form a positive electrode active layer. The total loading of 10,10'-[sulfonylbis(1,4-phenylene)]bis(10H-phenthiazine), Ketjen black, and PTFE is 10 mg / cm³. 2 The sample was placed in a drying oven and dried at 80°C for 360 minutes. Then it was cut and diced to obtain the positive electrode sheet of the aqueous organic zinc-ion battery.

[0060] Comparative Example 1 A positive electrode sheet for an aqueous organic zinc-ion battery is described. The difference between this comparative example and Example 1 is that the positive electrode active layer is phenazine, while the other components and preparation methods are the same.

[0061] Application Example 1 An aqueous organic zinc-ion battery, comprising, from top to bottom: a negative electrode shell 1, a negative electrode sheet 2 with a thickness of 0.1 mm, a separator 3 with a thickness of 0.7 mm, a positive electrode sheet 4 with a thickness of 0.55 mm, a gasket 5, a washer 6, and a positive electrode shell 7.

[0062] Wherein, the positive electrode 4 is the positive electrode of the aqueous organic zinc-ion battery described in Example 1; An electrolyte is disposed between the positive electrode 4 and the negative electrode 2, and the diaphragm 3 is wetted by the electrolyte.

[0063] The negative electrode 2 is a 100% pure zinc sheet polished with 1000-grit sandpaper; the diaphragm 3 is glass fiber; and the electrolyte is a Zn(OTF)2 aqueous solution with a concentration of 3 M.

[0064] The preparation method of the aqueous organic zinc-ion battery includes the following steps: Assemble the negative electrode shell, negative electrode sheet, separator, positive electrode sheet, gasket, and positive electrode shell in the order from top to bottom. Install 100% pure zinc sheet as the negative electrode sheet in the negative electrode shell. Add sufficient electrolyte until the separator is completely wetted. Then place the separator in the shell, with the positive electrode sheet with the slurry coating facing down so that it is in full contact with the separator. The current collector with the uncoated side facing up so that it is in contact with the gasket and completely covers the positive electrode sheet. Then place the gasket on the gasket and cover the positive electrode shell. After assembly, press and seal the assembly using a battery press to obtain an aqueous organic zinc-ion battery.

[0065] Application Example 2 An aqueous organic zinc-ion battery, comprising, from top to bottom: a negative electrode shell 1, a negative electrode sheet 2 with a thickness of 0.1 mm, a separator 3 with a thickness of 0.7 mm, a positive electrode sheet 4 with a thickness of 0.55 mm, a gasket 5, a washer 6, and a positive electrode shell 7.

[0066] Wherein, the positive electrode 4 is the positive electrode of the aqueous organic zinc-ion battery described in Example 2; An electrolyte is disposed between the positive electrode 4 and the negative electrode 2, and the diaphragm 3 is wetted by the electrolyte.

[0067] The negative electrode 2 is a 100% pure zinc sheet polished with 1000-grit sandpaper; the diaphragm 3 is glass fiber; and the electrolyte is a Zn(OTF)2 aqueous solution with a concentration of 3 M.

[0068] The preparation method of the aqueous organic zinc-ion battery includes the following steps: Assemble the negative electrode shell, negative electrode sheet, separator, positive electrode sheet, gasket, and positive electrode shell in the order from top to bottom. Install 100% pure zinc sheet as the negative electrode sheet in the negative electrode shell. Add sufficient electrolyte until the separator is completely wetted. Then place the separator in the shell, with the positive electrode sheet with the slurry coating facing down so that it is in full contact with the separator. The current collector with the uncoated side facing up so that it is in contact with the gasket and completely covers the positive electrode sheet. Then place the gasket on the gasket and cover the positive electrode shell. After assembly, press and seal the assembly using a battery press to obtain an aqueous organic zinc-ion battery.

[0069] Application Example 3 An aqueous organic zinc-ion battery, comprising, from top to bottom: a negative electrode shell 1, a negative electrode sheet 2 with a thickness of 0.1 mm, a separator 3 with a thickness of 0.7 mm, a positive electrode sheet 4 with a thickness of 0.55 mm, a gasket 5, a washer 6, and a positive electrode shell 7.

[0070] Wherein, the positive electrode 4 is the positive electrode of the aqueous organic zinc-ion battery described in Example 3; An electrolyte is disposed between the positive electrode 4 and the negative electrode 2, and the diaphragm 3 is wetted by the electrolyte.

[0071] The negative electrode 2 is a 100% pure zinc sheet polished with 1000-grit sandpaper; the diaphragm 3 is glass fiber; and the electrolyte is a Zn(OTF)2 aqueous solution with a concentration of 3 M.

[0072] The preparation method of the aqueous organic zinc-ion battery includes the following steps: Assemble the negative electrode shell, negative electrode sheet, separator, positive electrode sheet, gasket, and positive electrode shell in the order from top to bottom. Install 100% pure zinc sheet as the negative electrode sheet in the negative electrode shell. Add sufficient electrolyte until the separator is completely wetted. Then place the separator in the shell, with the positive electrode sheet with the slurry coating facing down so that it is in full contact with the separator. The current collector with the uncoated side facing up so that it is in contact with the gasket and completely covers the positive electrode sheet. Then place the gasket on the gasket and cover the positive electrode shell. After assembly, press and seal the assembly using a battery press to obtain an aqueous organic zinc-ion battery.

[0073] Comparative Application Example 1 An aqueous organic zinc-ion battery is described. The difference between this comparative application example and application example 1 is that the positive electrode is the positive electrode of the aqueous organic zinc-ion battery described in comparative example 1, while the other components and preparation methods are the same.

[0074] Test Example 1 The aqueous organic zinc-ion batteries prepared in Application Examples 1-3 and Comparative Application Example 1 were placed in an electrochemical workstation for testing their electrical performance.

[0075] Test method: Battery cycle performance: Set the working sequence: rest, constant current charging, constant current discharging, set the current density to 3 A / g, and set the number of cycles to 1200.

[0076] The battery cycle performance test results are shown in Table 1. Figure 3 The cycling performance of the aqueous organic zinc-ion battery prepared in Application Example 1 is shown. Figure 4 The cycling performance of the aqueous organic zinc-ion battery prepared in Application Example 2 is shown. Figure 5The cycling performance of the aqueous organic zinc-ion battery prepared in Application Example 3 is shown. Figure 6 The cycling performance of the aqueous organic zinc-ion battery prepared in Comparative Application Example 1 is shown in the diagram.

[0077] Table 1. Battery cycle performance test results of Application Examples 1-3 and Comparative Application Example 1 From Table 1 and Figure 3-6 As can be seen, the battery prepared in Application Example 1 has a charge-discharge specific capacity as high as 159.72 mAh / g, and after 1200 charge-discharge cycles, the specific capacity is 170.89 mAh / g. This demonstrates that using PXZ-DPS material as the active material of the positive electrode effectively enhances the battery's cycle stability. Application Examples 2 and 3 show similar performance to PXZ-DPS, exhibiting good stability and high capacity retention. However, compared to Application Example 1, their discharge capacity decays more rapidly, indicating insufficient structural stability or reaction reversibility, possibly due to the use of traditional or unoptimized materials, with a capacity retention of only 50.1%. In contrast, PXZ-DPS demonstrates outstanding performance: its discharge capacity decays extremely slowly during cycling, showing excellent structural stability and cycle life; simultaneously, its coulombic efficiency quickly reaches and remains stable at nearly 100% after initial break-in, and its capacity retention is also 100%. This directly proves the high reversibility of the electrochemical reaction and the crucial role of the sulfone group in suppressing side reactions and stabilizing active intermediates.

[0078] from Figure 3-6 It can be seen that as the number of cycles increases, both the discharge capacity and the charge capacity show a gradual decline trend, but the decline is relatively slow, indicating that the battery has good cycle stability. At the same time, the coulombic efficiency remains at a high level close to 100% throughout the entire cycle, indicating that the battery has excellent reversibility and a low degree of side reaction, good overall electrochemical performance, and 100% capacity retention after 1200 cycles.

[0079] Test Example 2 The battery rate performance corresponding to test cases 1-2 was tested, and the test results are shown in Table 2-3. Figure 7-8 As shown; Figure 7 The rate performance diagram of the aqueous organic zinc-ion battery prepared in Application Example 1 is shown. Figure 8 The rate performance diagram of the aqueous organic zinc-ion battery prepared in Application Example 2 is shown.

[0080] Table 2. Battery rate performance test results for Application Example 1 Table 3. Battery rate performance test results for Application Example 2 From Table 2-3 and Figure 7-8 As can be seen, the average charge / discharge specific capacity of the battery prepared in Example 1 at a series of high-rate current densities of 0.2 A / g, 0.5 A / g, 1 A / g, 3 A / g, 5 A / g, 7 A / g, 9 A / g, 10 A / g, 15 A / g, and 20 A / g are 250.57 mAh / g, 197.60 mAh / g, 179.14 mAh / g, 171.39 mAh / g, 162.73 mAh / g, 156.79 mAh / g, 151.51 mAh / g, 149.18 mAh / g, 140.00 mAh / g, and 132.72 mAh / g, respectively. Because PXZ-DPS is a fused-ring macromolecule, it exhibits a low coulombic efficiency at low current densities, but its activity gradually increases with increasing current density, and the coulombic efficiency remains at 99%. Application Example 2 exhibits similar performance to PXZ-DPS, showing low coulombic efficiency at low current densities, but its activity gradually increases with increasing current density, and the coulombic efficiency remains at 99%.

[0081] from Figure 7 The system exhibits good electrochemical activity in the initial stage, especially maintaining a high discharge capacity at higher rates, demonstrating its excellent rate performance potential. Simultaneously, the coulombic efficiency is close to 100% in the early stages of testing, indicating that the battery maintains good reversibility at high charge-discharge rates, reflecting good matching between the positive and negative electrode materials and the electrolyte, and relatively stable interfacial reactions. These data collectively demonstrate that the battery system possesses rapid charge-discharge capabilities, providing a positive research foundation and clear direction for further improvements in cycle stability and overall performance through optimization of electrode structure or electrolyte formulation.

[0082] The test results above show that the battery's charge-discharge specific capacity does not suffer much loss under high current density. Even in the last 10 cycles at a current density of 0.2 A / g, the average charge-discharge specific capacity is still 195.33 mAh / g. Although there is a slight decrease, the capacity remains above 190 mAh / g, indicating that the battery has excellent charge-discharge reversibility and demonstrates extremely high charge-discharge efficiency at high current density.

[0083] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0084] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A positive electrode sheet for an aqueous organic zinc-ion battery, characterized in that, The positive electrode of the aqueous organic zinc-ion battery includes a current collector and a positive electrode active layer disposed on the current collector; The positive electrode active layer includes a positive electrode organic active material, a conductive agent, and a binder; The positive electrode organic active material is selected from one or more of the following: phenazine aromatic heterocyclic compounds containing sulfone groups, phenothiazine aromatic heterocyclic compounds containing sulfone groups, phenotoxazine aromatic heterocyclic compounds containing sulfone groups, and phenotelezine aromatic heterocyclic compounds containing sulfone groups.

2. The positive electrode sheet of the aqueous organic zinc-ion battery according to claim 1, characterized in that, The positive electrode organic active material is selected from the following structures: ； R1 and R2 are selected from one or more of hydrogen atoms, phenazine aromatic heterocyclic compounds, phenoxazine aromatic heterocyclic compounds, phenselenidine aromatic heterocyclic compounds, and phenothiazine aromatic heterocyclic compounds; n1 is selected from 1-3; n2 is selected from 1-3; X is selected from one or more of S, N, O, and Se; R3 is selected from one or more of the following: phenazine aromatic heterocyclic compounds, phenoxazine aromatic heterocyclic compounds, phenselenidine aromatic heterocyclic compounds, and phenothiazine aromatic heterocyclic compounds.

3. The positive electrode sheet of the aqueous organic zinc-ion battery according to claim 1, characterized in that, The conductive agent is selected from one or more of carbon black, graphene, acetylene black, or Ketjen black.

4. The positive electrode sheet of the aqueous organic zinc-ion battery according to claim 1, characterized in that, The adhesive is selected from one or more of PTFE or PVDF.

5. The positive electrode sheet of the aqueous organic zinc-ion battery according to claim 1, characterized in that, The mass ratio of the positive electrode organic active material, conductive agent and binder is 1:(0.5-1.5):(0.1-1).

6. The method for preparing the positive electrode sheet of the aqueous organic zinc-ion battery according to any one of claims 1-5, characterized in that, Includes the following steps: S1. Mix the positive electrode organic active material, conductive agent and binder, grind them evenly to obtain a slurry; S2. The slurry is coated onto the current collector to form a positive electrode active layer, heated and dried, and then cut to obtain the positive electrode sheet of the aqueous organic zinc ion battery.

7. The method for preparing the positive electrode sheet of an aqueous organic zinc-ion battery according to claim 6, characterized in that, In step S2, the heating temperature is 45-200℃.

8. The method for preparing the positive electrode sheet of an aqueous organic zinc-ion battery according to claim 6, characterized in that, In step S2, the coating loading ranges from 0.5 to 20 mg / cm³. 2 .

9. An aqueous organic zinc-ion battery, characterized in that, The aqueous organic zinc-ion battery comprises, from top to bottom: a negative electrode shell, a negative electrode sheet, a separator, a positive electrode sheet, a gasket, a washer, and a positive electrode shell; Wherein, the positive electrode sheet is the positive electrode sheet of the aqueous organic zinc-ion battery according to any one of claims 1-5; An electrolyte is disposed between the positive electrode and the negative electrode, and the diaphragm is wetted by the electrolyte.

10. The aqueous organic zinc-ion battery according to claim 9, characterized in that, The electrolyte is selected from one or more of zinc sulfate solution, zinc trifluoromethanesulfonate solution, or zinc chloride solution.

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