A hydrogen ion battery with an organic material containing both carbonyl and imine groups as a negative electrode

Abstract

The application discloses a hydrogen ion battery with an organic material containing a carbonyl and imine group double active site as a negative electrode; the molecular structure of the organic material has a carbonyl and imine group double active site and a pi-pi conjugated structure, forms a stable skeleton with an extended conjugated system and abundant active sites, and solves the problems of single active site, low proton storage capacity and poor cycle stability of traditional organic electrode materials; the preparation method is simple in process, mild in conditions and high in product purity; the organic negative electrode material is matched with carbon black and a binder to form a negative electrode sheet, and is assembled into a full aqueous proton battery together with a sulfuric acid electrolyte and a manganese oxide positive electrode, and has the advantages of fast ion conduction rate, high safety, environmental friendliness, excellent rate performance and the like, effectively improves the discharge capacity and cycle life of the aqueous proton battery, and has a wide application prospect in the field of low-cost, high-safety energy storage devices.

Description

Technical Field

[0001] This invention relates to a hydrogen-ion battery, and more particularly to a hydrogen-ion battery using an organic material containing carbonyl and imine dual active sites as the negative electrode, belonging to the field of aqueous energy storage battery technology. Background Technology

[0002] With the increasing prominence of environmental and resource shortages, developing electrochemical energy storage systems with high energy density, high power density, and excellent long-cycle performance is of great significance to meet the energy storage needs of daily life and industry. Currently, Zn is one of the most studied metal ion carriers in aqueous batteries. 2+ K + Na + Non-metallic ion carriers include NH4+. 4+ H3O + However, these ions generally have large ionic radii, which limits their transport and insertion / extraction kinetics in electrode materials, thus restricting their application scenarios.

[0003] In recent years, hydrogen-ion batteries have gradually become a research hotspot. Hydrogen ions, due to their smallest ionic radius and lightest ionic mass, can achieve extremely fast transport kinetics, exhibiting significant advantages in high-rate, fast-response energy storage scenarios. In aqueous batteries, hydrogen ions achieve efficient insertion and extraction through the Grotthuss mechanism, enabling the battery to exhibit excellent rate performance. Prussian blue analogues, MoO3, WO3, and other substances have been proven to have proton storage capabilities in acidic electrolytes; however, these materials generally suffer from poor structural stability and poor cycle performance, severely limiting their further development and application. The previously reported PANQ organic electrode material, at 10 A g... -1 It can only cycle 100 times at a current density of 5 A g. -1 They can only cycle for 5000 cycles at the specified current density, all exhibiting poor electrochemical performance.

[0004] Organic electrode materials have become an important development direction in the field of sustainable electrochemical energy storage due to their advantages such as wide availability of raw materials, low cost, strong structural designability, and high theoretical energy density. Existing research has shown that organic compounds such as anthraquinone, benzoquinone, and phenazine can all achieve reversible proton storage. However, traditional organic electrode materials generally face bottlenecks such as easy solubility in electrolytes, low specific capacity, and poor long-cycle stability, making it difficult to meet the requirements of practical applications. Summary of the Invention

[0005] Purpose of the invention: The purpose of this invention is to provide a hydrogen ion battery with an organic material containing dual active sites of carbonyl and imine groups as the negative electrode, which can effectively improve the dissolution of materials in electrolytes, has high safety, stable structure and electrochemical performance during long cycles, and no significant capacity decay.

[0006] Technical Solution: The present invention relates to a hydrogen-ion battery using an organic material containing carbonyl and imine dual active sites as the negative electrode, which is an aqueous proton battery. The battery comprises a negative electrode sheet, an aqueous electrolyte, and a manganese oxide positive electrode. The negative electrode sheet contains an organic material containing carbonyl and imine dual active sites. The organic material is a compound shown in Formula I. The molecular structure of the organic negative electrode material has carbonyl (C=O) and imine (C=N) dual active sites, which can synergistically achieve reversible proton storage and deintercalation. .

[0007] The above-mentioned organic material containing dual active sites of carbonyl and imine groups is prepared by the following steps: 2,5-dihydroxy-p-benzoquinone and 2,3-diamino-1,4-naphthyldione are added to a reaction solvent, thoroughly stirred and mixed, and then placed in an oil bath at 40℃-200℃ for constant temperature stirring for 6-10 hours. After purification and vacuum drying, the organic material containing dual active sites of carbonyl and imine groups is obtained. The following is the general formula for the synthesis of the organic material: .

[0008] The molar ratio of 2,5-dihydroxy-p-benzoquinone to 2,3-diamino-1,4-naphthyldione is 1:1-10.

[0009] The reaction solvent is selected from one or more of the following: methanol, ethanol, acetic acid, dimethyl sulfoxide, water, acetonitrile, and dichloromethane.

[0010] The above-mentioned method for preparing the negative electrode sheet includes the following steps: organic materials containing carbonyl and imine dual active sites, carbon black and binder are mixed evenly in proportion, and after being prepared into a slurry, they are uniformly coated or loaded onto the surface of the current collector, and after drying, the negative electrode sheet of the aqueous proton battery is obtained.

[0011] The current collector is selected from one or more of the following: carbon paper, titanium mesh, titanium sheet, stainless steel mesh, stainless steel foil, carbon nanotube film, and graphene film.

[0012] The organic material containing carbonyl and imine dual active sites, carbon black and binder are in a weight ratio of 5-10:0-5:1, and the drying is vacuum drying at 60-80 °C for 12-24 h.

[0013] In the aforementioned hydrogen-ion battery using an organic material containing both carbonyl and imine active sites as the negative electrode, the aqueous electrolyte is a sulfuric acid electrolyte with a concentration of 0.5 M / L-2.5 M / L, and the manganese oxide positive electrode is a manganese oxide positive electrode. By using manganese oxide material as the positive electrode and sulfuric acid solution as the electrolyte, a complete battery is assembled to achieve highly safe and long-life aqueous energy storage.

[0014] Invention Principle: This invention relates to a hydrogen-ion battery using an organic material containing dual active sites of carbonyl and imine groups as the negative electrode, serving as an aqueous proton battery. The organic negative electrode material is composed of specially selected compounds, whose molecular structure contains dual active sites of carbonyl and imine groups. This material, with its highly planar aromatic conjugated system, effectively suppresses the dissolution, decomposition, and rearrangement of organic electrode materials during charge and discharge, avoiding the rapid capacity decay problem common to small molecule materials. The intermolecular hydrogen bond interaction network significantly enhances the structural rigidity of the material, effectively reducing its solubility tendency in acidic electrolytes, while simultaneously suppressing molecular skeleton collapse during charge-discharge cycles, thus improving structural stability. The carbonyl group and carbon-nitrogen double bond on the naphthoquinone core can undergo reversible proton coupling reactions, providing basic charge storage capacity. The planar fused ring structure enhances the π-π stacking interaction between molecules, improving electronic conductivity, while reducing the dissolution of active substances in the electrolyte, solving the problems of rapid cyclic decay and easy dissolution of traditional anthraquinones. Thanks to the dual active sites of carbonyl and imine groups, the organic anode material provided by this invention can achieve high specific capacity, excellent rate performance, and ultra-long cycle life when applied to aqueous hydrogen-ion batteries. The material of this invention exhibits higher molecular structural integrity and a significantly reduced capacity decay rate during long-cycle charge-discharge processes, effectively overcoming the core technical defect of poor cycle stability in existing organic electrode materials.

[0015] In this invention, the traditional ion intercalation is replaced by a "dissolution-deposition" type redox reaction, resulting in a more thorough reaction. During the charging process, Mn... 2+ MnO is oxidized and deposited on a carbon-based current collector, while H3O is generated simultaneously. + During the discharge process, MnO is reduced and dissolved back into Mn. 2+ Consume H3O + During the charging and discharging process at the positive electrode, H⁺ intercalation occurs. The negative electrode material contains multiple active sites, forming continuous H⁺ channels. H⁺ has a high diffusion coefficient, low migration barrier, and rapid kinetics, preventing dendrite formation during electrochemical reactions and ensuring structural stability, thereby increasing capacity.

[0016] Beneficial Effects: Compared with existing technologies, this invention has the following significant advantages: This invention uses a low-cost, synthesized organic material with quinone molecular characteristics as the negative electrode and inexpensive and readily available manganese oxide as the positive electrode to assemble an aqueous hydrogen-ion battery. Its organic negative electrode material has a highly planar aromatic system containing multiple active sites, significantly improving the specific capacity and charge transport kinetics per unit mass compared to organic electrode materials with single active sites, exhibiting superior rate performance. The presence of dual active sites (carbonyl and imine groups) and an intermolecular hydrogen bond network effectively enhances the material's structural rigidity, significantly reducing its solubility in acidic electrolytes, while suppressing molecular skeleton collapse during charge and discharge, greatly extending the battery's cycle life, with a capacity decay rate far lower than traditional organic electrode materials. This aqueous hydrogen-ion battery has a high specific capacity and a wide voltage window at a current density of 10 A g. -1 At that time, it can stably cycle more than 8,000 times, which is significantly better than most water-based hydrogen ion batteries. Attached Figure Description

[0017] Figure 1 This is a schematic diagram of the structure of the organic anode material containing carbonyl and imine dual active sites for hydrogen ion batteries prepared in Example 1. Figure 2 The image shows a scanning electron microscope (SEM) image of the organic anode material containing carbonyl and imine dual active sites for hydrogen ion batteries prepared in Example 1. Figure 3 The X-ray diffraction pattern of the organic anode material containing carbonyl and imine dual active sites for hydrogen ion batteries prepared in Example 1. Figure 4 Cyclic voltammetry curves of aqueous hydrogen-ion batteries assembled with electrode sheets were obtained using the organic negative electrode material containing carbonyl and imine dual active sites prepared in Example 1 as the electrode material. Figure 5 Cyclic voltammetry curves of aqueous hydrogen-ion batteries prepared using organic anode materials containing carbonyl and imine dual active sites prepared in Examples 1, 2, and 3 as electrode materials to prepare electrode sheets were obtained. Figure 6 The organic anode material containing carbonyl and imine dual active sites prepared in Example 1 was used as the electrode material to prepare an aqueous hydrogen-ion battery with electrode sheet assembly, and the long cycle performance curve was obtained. Figure 7 The charge-discharge performance curves of aqueous hydrogen-ion batteries assembled with electrode sheets are obtained by using organic anode materials containing carbonyl and imine dual active sites prepared in Examples 1, 2, and 3 as electrode materials. Figure 8 The performance of an aqueous hydrogen-ion battery assembled with electrode sheets prepared using the organic negative electrode material containing carbonyl and imine dual active sites prepared in Example 1 as the electrode material is compared with that of other reported aqueous hydrogen-ion batteries. Figure 9 This is a schematic diagram of the structure of a hydrogen-ion battery of the present invention, which uses an organic material containing carbonyl and imine dual active sites as the negative electrode. Detailed Implementation

[0018] The present invention will now be described in detail with reference to specific embodiments.

[0019] Example 1 An organic anode material containing dual active sites of carbonyl and imine groups for use in hydrogen-ion batteries is prepared through the following steps: 0.14 g of 2,5-dihydroxy-p-benzoquinone and 0.376 g of 2,3-diaminonaphthalene-1,4-dione were ground thoroughly in a mortar to obtain a premix. The premix was then added to 100 ml of glacial acetic acid and heated to 110 °C in an oil bath. The mixture was stirred for 6 hours. After the reaction was completed, the mixture was cooled to room temperature and poured out. It was centrifuged at 5000 r for 5 min. The resulting precipitate was washed successively with acetic acid, deionized water, and ethanol. Finally, it was dried in a vacuum drying oven at 100 °C for 24 hours to obtain an organic anode material containing carbonyl and imino dual active sites.

[0020] Example 2 An organic anode material containing dual active sites of carbonyl and imine groups for use in hydrogen-ion batteries is prepared through the following steps: 0.14 g of 2,5-dihydroxy-p-benzoquinone and 0.752 g of 2,3-diaminonaphthalene-1,4-dione were ground thoroughly in a mortar to obtain a premix. The premix was then added to 100 ml of glacial acetic acid and heated to 110 °C in an oil bath. The mixture was stirred for 6 hours. After the reaction was completed, the mixture was cooled to room temperature and poured out. It was centrifuged at 5000 r for 5 min. The resulting precipitate was washed successively with acetic acid, deionized water, and ethanol. Finally, it was dried in a vacuum drying oven at 100 °C for 24 hours to obtain an organic anode material containing carbonyl and imine dual active sites for hydrogen ion batteries.

[0021] Example 3 An organic anode material containing carbonyl and imine dual active sites for hydrogen ion batteries is prepared as follows: 0.14 g of 2,5-dihydroxy-p-benzoquinone and 1.128 g of 2,3-diaminonaphthalene-1,4-dione are placed in a mortar and ground thoroughly to obtain a premix. The premix is ​​then added to 100 ml of glacial acetic acid and heated to 110 °C in an oil bath. The mixture is stirred for 6 hours. After the reaction is complete, the mixture is cooled to room temperature and poured out. It is then centrifuged at 5000 r for 5 min. The resulting precipitate is washed successively with acetic acid, deionized water, and ethanol. Finally, it is placed in a vacuum drying oven and dried at 100 °C for 24 hours to obtain the organic anode material containing carbonyl and imine dual active sites for hydrogen ion batteries.

[0022] Example 4 The specific preparation steps of an aqueous hydrogen-ion battery are as follows: 6g of organic negative electrode material containing carbonyl and imine dual active sites for hydrogen ion batteries, 3g of acetylene black, and 1g of polyvinylidene fluoride were dispersed in 10g 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, an aqueous hydrogen ion battery was assembled using the electrode sheet as the working electrode, sulfuric acid solution (2M) as the electrolyte, a carbon rod as the counter electrode, and Ag / AgCl as the reference electrode.

[0023] Example 5 The specific preparation steps of an aqueous hydrogen-ion battery are as follows: 7g of organic negative electrode material containing carbonyl and imine dual active sites for hydrogen ion batteries, 2g of acetylene black, and 1g of polyvinylidene fluoride were dispersed in 15g 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, an aqueous hydrogen ion battery was assembled using the electrode sheet as the working electrode, sulfuric acid solution (2M) as the electrolyte, a carbon rod as the counter electrode, and Ag / AgCl as the reference electrode.

[0024] Example 6 The specific preparation steps of an aqueous hydrogen-ion battery are as follows: 8g of organic negative electrode material containing carbonyl and imine dual active sites for hydrogen ion batteries, 1g of acetylene black, and 1g of polyvinylidene fluoride were dispersed in 20g 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, an aqueous hydrogen ion battery was assembled using the electrode sheet as the working electrode, sulfuric acid solution (2M) as the electrolyte, a carbon rod as the counter electrode, and Ag / AgCl as the reference electrode.

[0025] Performance testing: The aqueous hydrogen ion batteries assembled in Examples 4-6 were subjected to charge-discharge performance testing using an electrochemical workstation and a charge-discharge tester.

[0026] Data analysis: such as Figure 2 As shown, the organic anode material containing carbonyl and imine dual active sites for hydrogen ion batteries prepared in Example 1 exhibits an irregular blocky structure. This morphological feature is beneficial for the exposure of active sites and simultaneously increases the contact area with the electrolyte, allowing the organic anode material containing carbonyl and imine dual active sites for hydrogen ion batteries to fully react during chemical reactions. Figure 3 As shown, the organic anode material containing carbonyl and imine dual active sites for hydrogen ion batteries described in Example 1 was successfully synthesized and has moderate crystallinity. It also shows that the organic anode material containing carbonyl and imine dual active sites for hydrogen ion batteries has a stable structure and good proton transport capability.

[0027] like Figure 4 As shown, the electrode sheet prepared using the organic negative electrode material containing carbonyl and imine dual active sites for hydrogen ion batteries prepared in Example 1 is used as the electrode material in the assembly of an aqueous hydrogen ion battery. The DPD electrode and manganese oxide are used at 1 mV·s -1 Cyclic voltammetry curves at scan rate. For example... Figure 5 As shown, the cyclic voltammetry curves of an aqueous hydrogen-ion battery assembled using an electrode sheet prepared with an organic anode material containing carbonyl and imine dual active sites (as described in Example 1) at different scan rates on the same device show that the CV curves of this battery exhibit obvious redox peaks at different scan rates, indicating that the electrode sheet has good redox activity. Figure 6 As shown, the electrode sheet prepared by the organic negative electrode material containing carbonyl and imine dual active sites for hydrogen ion batteries in Example 1, when used as the electrode material in the assembled aqueous hydrogen ion battery, did not show a significant decrease in capacity after 10,000 charge-discharge cycles, indicating that the electrode sheet has excellent stability. It also reflects that the negative electrode material has a pp conjugation effect, which improves the rigidity of the molecules and effectively alleviates the problem of easy dissolution of the material, thus giving the electrode material good cycle stability.

[0028] like Figure 7As shown, compared with the organic negative electrode material containing carbonyl and imine dual active sites used in Example 2 for hydrogen ion batteries, the aqueous hydrogen ion battery assembled with electrode sheets prepared by Example 1 exhibits a higher charge and discharge capacity. In Example 1, 2,3-diaminonaphthalene-1,4-dione and dihydroxybenzoquinone are mixed and reacted in a molar ratio of 2:1. The two monomers undergo Schiff base reaction with very few byproducts, basically only water. The product is purer and has high atom utilization, thus enabling the aqueous hydrogen ion battery using this material as the electrode material to exhibit excellent electrochemical performance.

[0029] like Figure 8 As shown, the aqueous hydrogen-ion battery prepared by using an organic anode material containing carbonyl and imine dual active sites as the electrode material in Example 1 for hydrogen-ion batteries, compared with other reported aqueous hydrogen-ion batteries, has significantly better long-cycle performance and capacity retention than the other reported aqueous hydrogen-ion batteries, showing superior cycle performance and laying the foundation for its subsequent practical application.

[0030] Therefore, the hydrogen ion battery of the present invention uses an organic material containing carbonyl and imine dual active sites as the negative electrode. By using an organic material with carbonyl and imine dual active sites and a π-π conjugated structure as the negative electrode, a stable framework with an extended conjugated system and abundant active sites is formed, which solves the problems of single active sites, low proton storage capacity and poor cycle stability of traditional organic electrode materials.

Claims

1. A hydrogen-ion battery using an organic material containing both carbonyl and imine active sites as the negative electrode, characterized in that, The hydrogen-ion battery is an aqueous proton battery, consisting of a negative electrode, an aqueous electrolyte, and a manganese oxide positive electrode. The negative electrode contains an organic material with dual active sites of carbonyl and imine groups, and the organic material is a compound of formula I. 。 2. The hydrogen-ion battery according to claim 1, using an organic material containing both carbonyl and imine active sites as the negative electrode, is characterized in that... The organic material containing dual active sites of carbonyl and imine groups is prepared by the following steps: 2,5-dihydroxy-p-benzoquinone and 2,3-diamino-1,4-naphthyldione are added to a reaction solvent, thoroughly stirred and mixed, and then placed in an oil bath at 40℃-200℃ for constant temperature stirring for 6-10 hours. After purification and vacuum drying, the organic material containing dual active sites of carbonyl and imine groups is obtained. The following is the general formula for the synthesis of the organic material:

3. The hydrogen-ion battery according to claim 2, using an organic material containing both carbonyl and imine active sites as the negative electrode, is characterized in that... The molar ratio of 2,5-dihydroxy-p-benzoquinone to 2,3-diamino-1,4-naphthyldione is 1:1-10.

4. The hydrogen-ion battery according to claim 2, using an organic material containing both carbonyl and imine active sites as the negative electrode, is characterized in that... The reaction solvent is selected from one or more of the following: methanol, ethanol, acetic acid, dimethyl sulfoxide, water, acetonitrile, and dichloromethane.

5. The hydrogen-ion battery according to claim 1, using an organic material containing both carbonyl and imine active sites as the negative electrode, is characterized in that... The method for preparing the negative electrode sheet includes the following steps: mixing organic materials containing carbonyl and imine dual active sites, carbon black and binder in proportion, preparing a slurry, uniformly coating or loading it onto the surface of the current collector, and drying it to obtain the negative electrode sheet of the aqueous proton battery.

6. The hydrogen-ion battery according to claim 5, using an organic material containing both carbonyl and imine active sites as the negative electrode, is characterized in that... The current collector is selected from one or more of the following: carbon paper, titanium mesh, titanium sheet, stainless steel mesh, stainless steel foil, carbon nanotube film, and graphene film.

7. The hydrogen-ion battery according to claim 5, using an organic material containing both carbonyl and imine active sites as the negative electrode, is characterized in that... The weight ratio of the organic material containing carbonyl and imine dual active sites, carbon black, and binder is 5-10:0-5:

1.

8. The hydrogen-ion battery according to claim 5, using an organic material containing both carbonyl and imine active sites as the negative electrode, is characterized in that... The drying conditions are vacuum drying at 60~80 ℃ for 12~24 h.

9. The hydrogen-ion battery according to claim 1, using an organic material containing both carbonyl and imine active sites as the negative electrode, is characterized in that... The concentration of the aqueous electrolyte is 0.5 M / L-2.5 M / L.

10. The hydrogen-ion battery according to claim 1, using an organic material containing both carbonyl and imine active sites as the negative electrode, is characterized in that... The aqueous electrolyte is a sulfuric acid electrolyte, and the positive electrode is a manganese oxide positive electrode.

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