A polyquinopamine positive electrode material, a preparation method and application thereof
By preparing polyquinone amine cathode materials, the problems of low capacity utilization and unsatisfactory cycle performance in multivalent ion batteries have been solved, and good cycle stability and high-efficiency electrochemical performance in zinc-ion batteries have been achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- YANSHAN UNIV
- Filing Date
- 2023-09-05
- Publication Date
- 2026-05-12
AI Technical Summary
Existing organic cathode materials exhibit low capacity utilization, rapid capacity decay during charge and discharge, and unsatisfactory cycle performance in multivalent ion batteries.
The preparation method of polyquinone amine cathode material involves heating and condensing 2,3,4,6-tetrachlorobenzoquinone with 1,2-cyclohexanediamine under inert gas protection, followed by filtration, washing and drying to obtain a black solid powder.
Polyquinone amine cathode material exhibits good cycle reversibility and rate performance in zinc-ion batteries, with a first-cycle discharge specific capacity of 187 mAh g-1 and a capacity retention rate of 48% after 200 charge-discharge cycles.
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Figure CN117143336B_ABST
Abstract
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, organic cathode materials mainly exhibit certain application performance in lithium-ion, sodium-ion, and potassium-ion batteries. However, the number of organic cathode material structures suitable for multivalent ion batteries is relatively small. In multivalent ion batteries, the capacity and cycle performance of organic cathode materials are not ideal, exhibiting characteristics such as low actual specific capacity and rapid capacity decay during charge and discharge. Given the rich variety and relatively complex three-dimensional configurations of organic materials, designing and developing novel organic cathode materials with structures more suitable for the intercalation and deintercalation of multivalent ions is of great significance for promoting their development and large-scale 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] The present invention also provides a method for preparing the polyquinone amine cathode material, the method comprising the following steps: dissolving 2,3,4,6-tetrachlorobenzoquinone and 1,2-cyclohexanediamine in a reaction solvent, and heating under inert gas protection to carry out a condensation reaction; after the reaction is completed, filtering is performed to obtain a filter cake; the filter cake is washed with a washing solvent and then dried to obtain the organic cathode material.
[0009] Furthermore, the method specifically includes the following steps: 2,3,4,6-tetrachlorobenzoquinone and 0.28 g to 0.65 g of 1,2-cyclohexanediamine are dissolved in a reaction solvent at a ratio of 5 mL to 200 mL per gram of 2,3,4,6-tetrachlorobenzoquinone and 1,2-cyclohexanediamine, and reacted at 40 °C to 150 °C for 1 h to 48 h under inert gas protection; after the reaction is completed and cooled, the mixture 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, n-butanol, pyridine, N,N-dimethylformamide, or N-methylpyrrolidone.
[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, N,N-dimethylformamide, 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 cathode material, its preparation method, and its applications. This polyquinone amine 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. The preparation method of this organic cathode material is simple and feasible. Experiments have shown that when this polyquinone amine cathode material is applied to zinc-ion batteries, it exhibits good cycle reversibility and rate performance at 0.02 Ag. -1 The first-cycle discharge specific capacity can reach 187 mAh g at the current density. -1 After 200 charge-discharge cycles, the discharge specific capacity remained at 90 mAh g. -1 . 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 4 Thermogravimetric spectrum of the polyquinone amine cathode material prepared in Example 1 of this invention;
[0021] Figure 5 This is a cyclic voltammetry curve of the polyquinone amine cathode material prepared in Example 1 of the present invention in a zinc-ion battery;
[0022] Figure 6 The polyquinone amine cathode material prepared in Example 1 of this invention was used in a zinc-ion battery at 0.02 Ag. -1 0.05Ag -1 0.1Ag -1 0.2Ag -1 0.5Ag -1 1Ag -1 and 0.02Ag -1 Rate performance at current density;
[0023] Figure 7 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 Long-cycle diagram of 200 charge-discharge cycles at current density. Detailed Implementation
[0024] As can be seen from the background technology, organic cathode materials in multivalent ion batteries currently have unsatisfactory electrochemical performance in terms of specific capacity utilization, rate capability, and long cycle life, such as low actual specific capacity and rapid capacity decay during charge and discharge.
[0025] This invention provides an organic cathode material, the structural formula of which is:
[0026] Where n is a natural number greater than or equal to 1.
[0027] The present invention also provides a method for preparing the organic cathode material, the method comprising the following steps: dissolving 2,3,4,6-tetrachlorobenzoquinone and 1,2-cyclohexanediamine in a reaction solvent, and heating under inert gas protection to carry out a condensation reaction; after the reaction is completed, filtering is performed to obtain a filter cake; the filter cake is washed with a washing solvent and then dried to obtain the organic cathode material.
[0028] The synthetic route for this reaction is shown below:
[0029]
[0030] Furthermore, the method specifically includes the following steps: 2,3,4,6-tetrachlorobenzoquinone and 0.28 g to 0.65 g of 1,2-cyclohexanediamine are dissolved in a reaction solvent at a ratio of 5 mL to 200 mL per gram of 2,3,4,6-tetrachlorobenzoquinone and 1,2-cyclohexanediamine, and reacted at 40 °C to 150 °C for 1 h to 48 h under inert gas protection; after the reaction is completed and cooled, the mixture 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.
[0031] Furthermore, the reaction solvent is methanol, ethanol, isopropanol, n-butanol, pyridine, N,N-dimethylformamide, or N-methylpyrrolidone.
[0032] Furthermore, the inert gas is nitrogen, helium, or argon.
[0033] Furthermore, the washing solvent is one or more of methanol, ethanol, isopropanol, n-butanol, N,N-dimethylformamide, and water.
[0034] This invention also provides the application of the organic cathode material described above in the field of ion batteries.
[0035] The present invention will now be described in detail with reference to specific embodiments.
[0036] Example 1
[0037] 0.300 g (i.e., 1.2 mmol) of 2,3,4,6-tetrachlorobenzoquinone and 0.182 g (i.e., 1.6 mmol) of 1,2-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.
[0038] Figure 1 The image shows the X-ray diffraction pattern of the polyquinone amine cathode material prepared in this embodiment. The main diffraction peak is a broad peak at 25°, indicating that the polyquinone amine cathode material in the invention is amorphous.
[0039] Figure 2 The image shows a scanning electron microscope (SEM) image of the polyquinone amine cathode material prepared in this embodiment, which exhibits a microsphere particle distribution at the micrometer scale.
[0040] 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 1228 cm⁻¹. -1 1614cm -1 2900cm -1 2987cm-1 and 3211cm -1 ~3385cm -1 .
[0041] Figure 4 The thermogravimetric spectrum of the organic cathode material prepared in this embodiment shows a significant mass loss after 300°C.
[0042] 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.
[0043] Figure 5 The polyquinone amine cathode material prepared in Example 1 of this invention is used in zinc-ion batteries at 0.1 mV s. -1 0.2mVs -1 0.3mV s -1 0.4mV s -1 0.5mV s -1 0.6mV s -1 0.8mV s -1 and 1mV s -1 Cyclic voltammetry curves at different scan rates. The oxidation peak is located at approximately 0.75 V, and the reduction peak is located at approximately 0.5 V.
[0044] Figure 6 The organic cathode material prepared in this embodiment is used in zinc-ion batteries at 0.02Ag. -1 0.05Ag -1 0.1Ag -1 0.2Ag -1 0.5Ag -1 1Ag -1 and 0.02Ag -1 Rate performance at current density. At 0.02Ag -1 At current density, the discharge specific capacity remains stable at 160 mAh g. -1 Around 1.0 Ag, the current density increases to 1.0 Ag. -1 The discharge capacity decreased to 22 mAh g. -1 When the current density drops back to 0.02Ag -1 At that time, the discharge specific capacity can be restored to a maximum of 140mAh g. -1 .
[0045] Figure 7 The organic cathode material prepared in this embodiment is used in a zinc-ion battery at a concentration of 0.02 Ag. -1 Long-cycle diagram at current density: first-cycle discharge specific capacity reaches 187 mAh g. -1 After 200 charge-discharge cycles, the capacity retention rate was 48%.
[0046] The electrochemical performance obtained from the above tests, such as discharge specific capacity, rate performance stability, and long-cycle capacity retention, is superior to that of existing cathode materials such as poly(1,4-benzoquinone-ethylenediamine) and poly(1,4-benzoquinone-urea).
[0047] Example 2
[0048] 0.300 g (i.e., 1.2 mmol) of 2,3,4,6-tetrachlorobenzoquinone and 0.195 g (i.e., 1.7 mmol) of 1,2-cyclohexanediamine were dissolved in 60 mL of methanol and reacted at 40 °C for 48 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 ethanol and then dried to obtain a black solid powder, which is the polyquinone amine cathode material of the present invention.
[0049] Example 3
[0050] 0.300 g (i.e., 1.2 mmol) of 2,3,4,6-tetrachlorobenzoquinone and 0.195 g (i.e., 1.6 mmol) of 1,2-cyclohexanediamine were dissolved in 10 mL of N,N-dimethylformamide and reacted at 140 °C for 1 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.
[0051] Example 4
[0052] 0.300 g (i.e., 1.2 mmol) of 2,3,4,6-tetrachlorobenzoquinone and 0.085 g (i.e., 0.7 mmol) of 1,2-cyclohexanediamine were dissolved in 20 mL of pyridine and reacted at 110 °C for 4 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 N,N-dimethylformamide and water and then dried to obtain a black solid powder, which is the polyquinone amine cathode material of the present invention.
[0053] 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 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: 2,3,4,6-Tetrachlorobenzoquinone and 1,2-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 0.28 g to 0.65 g of 1,2-cyclohexanediamine dissolved in 5 mL to 200 mL of reaction solvent, 2,3,4,6-tetrachlorobenzoquinone and 1,2-cyclohexanediamine were dissolved in the reaction solvent and reacted at 40 °C to 150 °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, n-butanol, pyridine, N,N-dimethylformamide, or N-methylpyrrolidone.
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, N,N-dimethylformamide, and water.
7. The application of the polyquinone amine cathode material as described in claim 1 in the field of ion batteries.