A polyquinopamine-based positive electrode material, a preparation method and application thereof

Abstract

The application provides a polyquinamine positive electrode material and a preparation method and application thereof. The preparation method of the polyquinamine positive electrode material comprises the following steps: 2,5-dihydroxy-3,6-dichlorobenzoquinone and 1,4-cyclohexanediamine are dissolved in a reaction solvent, and a condensation reaction is carried out under the protection of an inert gas; after the reaction is completed, suction filtration is carried out to obtain a filter cake; the filter cake is washed with a washing solvent and then dried to obtain the polyquinamine positive electrode material.

Description

Technical Field

[0001] This invention relates to the field of battery technology, specifically to a polyquinone amine cathode material, its preparation method, and its application. Background Technology

[0002] Cathode materials are a key component of ion batteries, determining their electrochemical performance. The most widely used cathode materials are inorganic materials such as iron-based, manganese-based, and vanadium-based compounds. Organic cathode materials, however, are an emerging class of energy storage materials with advantages such as abundant resources, designable structures, easy large-scale production, and convenient degradation and recycling. Developing organic cathode materials aligns with the needs and application trends of current novel energy storage technologies and is an important means to replace metal mineral resources and develop new energy storage devices. Organic cathode materials are expected to become ideal cathode materials for ion batteries, demonstrating enormous application potential in the field of energy storage.

[0003] Currently, the development of organic cathode materials is in its early stages. Some organic cathode materials have achieved certain performance results in lithium-ion and sodium-ion batteries, but their application in multivalent ion batteries is relatively limited. Organic materials have rich structures and relatively complex three-dimensional configurations, making them easy to mass-produce. Designing and developing new structures and configurations of organic cathode materials is of great significance for promoting their development and application. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a polyquinone amine cathode material, its preparation method, and its applications.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] This invention provides a polyquinone amine cathode material, the structural formula of which is:

[0007] Where n is a natural number greater than or equal to 1.

[0008] This invention also provides a method for preparing a polyquinone amine cathode material, the method comprising the following steps: dissolving 2,5-dihydroxy-3,6-dichlorobenzoquinone and 1,4-cyclohexanediamine in a reaction solvent, and heating under inert gas protection to carry out a condensation reaction; after the reaction is completed, filtering to obtain a filter cake; washing the filter cake with a washing solvent and drying it to obtain the polyquinone amine cathode material.

[0009] Furthermore, the method specifically includes the following steps: 2,5-dihydroxy-3,6-dichlorobenzoquinone and 0.32-0.77 g of 1,4-cyclohexanediamine are dissolved in a reaction solvent at a ratio of 5 mL to 200 mL per gram of 2,5-dihydroxy-3,6-dichlorobenzoquinone and 1,5-cyclohexanediamine, respectively. The mixture is then reacted at 40°C to 120°C for 1 h to 48 h under inert gas protection. After the reaction is complete and the mixture is cooled, it is filtered to obtain a filter cake. The filter cake is washed with a washing solvent and then dried to obtain a black solid powder, which is the polyquinone amine cathode material.

[0010] Furthermore, the reaction solvent is methanol, ethanol, isopropanol, or n-butanol.

[0011] Furthermore, the inert gas is nitrogen, helium, or argon.

[0012] Furthermore, the washing solvent is one or more of methanol, ethanol, isopropanol, n-butanol, and water.

[0013] This invention also provides the application of the polyquinone amine cathode material described above in the field of ion batteries.

[0014] Compared with the prior art, the technical solution provided by the present invention has at least the following advantages:

[0015] This invention provides a polyquinone amine-based cathode material, its preparation method, and its applications. This polyquinone amine-based cathode material possesses a specific microstructure, allowing for more stable intercalation of multivalent ions, and is poorly soluble in electrolytes, effectively suppressing the loss of active materials. This polyquinone amine-based cathode material belongs to the organic cathode material category, enabling large-scale production. Compared to inorganic cathode materials, it is more easily degraded, which is of great significance for promoting the development of clean energy storage materials. Attached Figure Description

[0016] One or more embodiments are illustrated by way of example with reference to the accompanying drawings. These illustrations do not constitute a limitation on the embodiments, and unless otherwise stated, the figures in the drawings are not to be limited by scale.

[0017] Figure 1 The X-ray diffraction pattern of the polyquinone amine cathode material prepared in Example 1 of this invention;

[0018] Figure 2 This is a scanning electron microscope image of the polyquinone amine cathode material prepared in Example 1 of the present invention;

[0019] Figure 3 The infrared spectrum of the polyquinone amine cathode material prepared in Example 1 of this invention;

[0020] Figure 4This is a cyclic voltammetry curve of the polyquinone amine cathode material prepared in Example 1 of the present invention in a zinc-ion battery;

[0021] Figure 5 The polyquinone amine cathode material prepared in Example 1 of this invention was used in a zinc-ion battery at a concentration of 0.02 Ag. -1 0.05Ag -1 0.1Ag -1 0.2Ag -1 0.5Ag -1 and 1Ag -1 Charge-discharge curves at current density. Detailed Implementation

[0022] As can be seen from the background technology, the application of organic cathode materials in ion batteries is relatively limited, especially in multivalent ion battery applications, where the performance of organic cathode materials is even less than ideal.

[0023] This invention provides a polyquinone amine cathode material, the structural formula of which is:

[0024] Where n is a natural number greater than or equal to 1.

[0025] This invention also provides a method for preparing a polyquinone amine cathode material, the method comprising the following steps: dissolving 2,5-dihydroxy-3,6-dichlorobenzoquinone and 1,4-cyclohexanediamine in a reaction solvent, and heating under inert gas protection to carry out a condensation reaction; after the reaction is completed, filtering to obtain a filter cake; washing the filter cake with a washing solvent and drying it to obtain the polyquinone amine cathode material.

[0026] Furthermore, the method specifically includes the following steps: 2,5-dihydroxy-3,6-dichlorobenzoquinone and 0.32-0.77 g of 1,4-cyclohexanediamine are dissolved in a reaction solvent at a ratio of 5 mL to 200 mL per gram of 2,5-dihydroxy-3,6-dichlorobenzoquinone and 1,5-cyclohexanediamine, respectively. The mixture is then reacted at 40°C to 120°C for 1 h to 48 h under inert gas protection. After the reaction is complete and the mixture is cooled, it is filtered to obtain a filter cake. The filter cake is washed with a washing solvent and then dried to obtain a black solid powder, which is the polyquinone amine cathode material.

[0027] The synthetic route for this reaction is shown below:

[0028]

[0029] Furthermore, the reaction solvent is methanol, ethanol, isopropanol, or n-butanol.

[0030] Furthermore, the inert gas is nitrogen, helium, or argon.

[0031] Furthermore, the washing solvent is one or more of methanol, ethanol, isopropanol, n-butanol, and water.

[0032] This invention also provides the application of the polyquinone amine cathode material described above in the field of ion batteries.

[0033] The present invention will now be described in detail with reference to specific embodiments.

[0034] Example 1

[0035] 0.249 g (i.e., 1.2 mmol) of 2,5-dihydroxy-3,6-dichlorobenzoquinone and 0.182 g (i.e., 1.6 mmol) of 1,4-cyclohexanediamine were dissolved in 25 mL of ethanol and reacted at 78 °C for 24 h under nitrogen protection. After the reaction was completed and cooled, the mixture was filtered to obtain a filter cake. The filter cake was washed three times with water and ethanol and then dried to obtain a black solid powder, which is the polyquinone amine cathode material of the present invention.

[0036] Figure 1 The image shows the X-ray diffraction pattern of the polyquinone amine cathode material prepared in this embodiment. The figure shows a broad peak at around 22°, which is not obvious, indicating that the polyquinone amine cathode material in the invention is amorphous.

[0037] Figure 2 The image shows a scanning electron microscope (SEM) image of the polyquinone amine cathode material prepared in this embodiment, which exhibits an irregular blocky distribution at the micrometer scale.

[0038] Figure 3 The image shows the infrared spectrum of the polyquinone amine cathode material prepared in this embodiment. The main absorption peak range is around 1250 cm⁻¹. -1 1394cm -1 1507cm -1 2901cm -1 2987cm -1 and 3230cm -1 ~3370cm -1 .

[0039] The polyquinone amine cathode material prepared in this embodiment was used as the active material for the positive electrode of a zinc-ion battery. The cathode material, acetylene black, and polyvinylidene fluoride were mixed and ground in a mass ratio of 6:3:1. N-methylpyrrolidone was added dropwise during grinding, and the mixture was coated onto a stainless steel mesh and vacuum dried to form a positive electrode sheet. A zinc sheet was used as the negative electrode. 1 mol L -1 A CR2032 coin cell was assembled using ZnSO4 solution as the electrolyte and glass fiber as the separator, and its electrochemical performance was tested.

[0040] Figure 4The polyquinone amine cathode material prepared in Example 1 of this invention is used in zinc-ion batteries at 1 mV s. -1 Cyclic voltammetry curves at different scan rates. The oxidation peak is located at approximately 0.8 V, and the reduction peak is located at approximately 0.6 V.

[0041] Figure 5 The polyquinone amine cathode material prepared in this embodiment is used in a zinc-ion battery at 0.02 Ag. -1 0.05Ag -1 0.1Ag -1 0.2Ag -1 0.5Ag -1 and 1Ag -1 The charge-discharge curve at the current density corresponds to a discharge specific capacity of 88 mAh g. -1 77mAh g -1 65mAh g -1 39mAh g -1 19mAh g -1 and 13mAh g -1 .

[0042] Example 2

[0043] 0.208 g (i.e., 1 mmol) of 2,5-dihydroxy-3,6-dichlorobenzoquinone and 0.159 g (i.e., 1.4 mmol) of 1,4-cyclohexanediamine were dissolved in 40 mL of n-butanol and reacted at 110 °C for 1 h under argon protection. After the reaction was completed and cooled, the mixture was filtered to obtain a filter cake. The filter cake was washed three times with water and n-butanol and then dried to obtain a black solid powder, which is the polyquinone amine cathode material of the present invention.

[0044] According to the ratio of 0.32 g to 0.77 g of 1,4-cyclohexanediamine dissolved in 5 mL to 200 mL of reaction solvent, 2,5-dihydroxy-3,6-dichlorobenzoquinone and 1,5-cyclohexanediamine were dissolved in the reaction solvent and reacted at 40 °C to 120 °C for 1 h to 48 h under inert gas protection. After the reaction was completed and cooled, the mixture was filtered to obtain a filter cake. The filter cake was washed with washing solvent and dried to obtain a black solid powder, which is the polyquinone amine cathode material.

[0045] Example 3

[0046] 0.208 g (i.e., 1 mmol) of 2,5-dihydroxy-3,6-dichlorobenzoquinone and 0.068 g (i.e., 0.6 mmol) of 1,4-cyclohexanediamine were dissolved in 10 mL of methanol and reacted at 40 °C for 48 h under helium protection. After the reaction was completed and cooled, the mixture was filtered to obtain a filter cake. The filter cake was washed three times with methanol and water and then dried to obtain a black solid powder, which is the polyquinone amine cathode material of the present invention.

[0047] Example 4

[0048] 0.208 g (i.e., 1 mmol) of 2,5-dihydroxy-3,6-dichlorobenzoquinone and 0.068 g (i.e., 0.6 mmol) of 1,4-cyclohexanediamine were dissolved in 20 mL of isopropanol and reacted at 80 °C for 24 h under nitrogen protection. After the reaction was completed and cooled, the mixture was filtered to obtain a filter cake. The filter cake was washed three times with isopropanol and water and then dried to obtain a black solid powder, which is the polyquinone amine cathode material of the present invention.

[0049] Those skilled in the art will understand that the above-described embodiments are specific examples of implementing this application, and in practical applications, various changes in form and detail may be made without departing from the spirit and scope of this application. Any person skilled in the art can make their own modifications and alterations without departing from the spirit and scope of this application; therefore, the scope of protection of this application should be determined by the scope defined in the claims.

Claims

1. A polyquinone amine-based cathode material, characterized in that, The structural formula of the polyquinone amine cathode material is as follows: ; where n is a natural number greater than 1.

2. The method for preparing the polyquinone amine cathode material according to claim 1, characterized in that, The method includes the following steps: 2,5-Dihydroxy-3,6-dichlorobenzoquinone and 1,4-cyclohexanediamine were dissolved in a reaction solvent and heated under inert gas protection to carry out a condensation reaction. After the reaction was completed, the mixture was filtered to obtain a filter cake. The filter cake was washed with a washing solvent and then dried to obtain the polyquinone amine cathode material.

3. The method for preparing the polyquinone amine cathode material according to claim 2, characterized in that, The method specifically includes the following steps: According to the ratio of 0.32 g to 0.77 g of 1,4-cyclohexanediamine dissolved in 5 mL to 200 mL of reaction solvent, 2,5-dihydroxy-3,6-dichlorobenzoquinone and 1,5-cyclohexanediamine were dissolved in the reaction solvent and reacted at 40 °C to 120 °C for 1 h to 48 h under inert gas protection. After the reaction was completed and cooled, the mixture was filtered to obtain a filter cake. The filter cake was washed with washing solvent and dried to obtain a black solid powder, which is the polyquinone amine cathode material.

4. The method for preparing the polyquinone amine cathode material according to claim 3, characterized in that, The reaction solvent is methanol, ethanol, isopropanol, or n-butanol.

5. The method for preparing the polyquinone amine cathode material according to claim 3, characterized in that, The inert gas is nitrogen, helium, or argon.

6. The method for preparing the polyquinone amine cathode material according to claim 3, characterized in that, The washing solvent is one or more of methanol, ethanol, isopropanol, n-butanol, and water.

7. The application of the polyquinone amine cathode material as described in claim 1 in the field of ion batteries.

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