Polyquinopamine organic positive electrode material and preparation method thereof
By preparing polyquinone amine organic cathode materials, the problems of low specific capacity and rapid capacity decay during charge and discharge in multivalent ion batteries were solved, and high efficiency, cycle reversibility, and rate performance in zinc-ion batteries were 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 have low specific capacity, rapid capacity decay during charge and discharge, and complex structures in multivalent ion batteries, making it difficult to meet the requirements of multivalent ion intercalation and deintercalation.
A method for preparing polyquinone amine organic cathode materials was adopted, which involves the oxidative addition reaction of 1,4-benzoquinone and 1,2-cyclohexanediamine or the condensation reaction of 2,5-dichloro-1,4-benzoquinone and 1,2-cyclohexanediamine to prepare polyquinone amine materials with specific microstructures for use in multivalent ion batteries.
Polyquinone amine organic cathode material exhibits good cycle reversibility and rate performance in zinc-ion batteries. The highest discharge specific capacity reaches 138 mAh g-1 at a current density of 0.02 A g-1, and the discharge specific capacity remains at 78 mAh g-1 after 200 charge-discharge cycles.
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Figure CN117143335B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of battery technology, specifically to a polyquinone amine organic cathode material and its preparation method. 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, organic cathode materials suffer from low specific capacity and rapid capacity decay during charge and discharge. Given the rich variety and relatively complex three-dimensional configurations of organic materials, developing novel organic cathode materials with structures more suitable for the intercalation and deintercalation of multivalent ions is of great significance for promoting the development and application of organic cathode materials. Summary of the Invention
[0004] To address the aforementioned technical problems, this invention provides a polyquinone amine organic cathode material and its preparation method.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0006] This invention provides a polyquinone amine organic 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 organic cathode material, the method comprising the following steps: dissolving 1,4-benzoquinone and 1,2-cyclohexanediamine in reaction solvent A and carrying out an oxidative addition reaction; after the reaction is completed, filtration is performed to obtain a filter cake; the filter cake is washed with a washing solvent and then dried to obtain the polyquinone amine organic cathode material.
[0009] Furthermore, the method specifically includes the following steps: 1,4-benzoquinone and 1,2-cyclohexanediamine are dissolved in reaction solvent A at a ratio of 10 mL to 200 mL per gram of 1,4-benzoquinone to 0.3 g to 1.3 g of 1,2-cyclohexanediamine; 0 mL of 1,4-benzoquinone and 1,2-cyclohexanediamine are bubbled into reaction solvent A at a ratio of 0 min per mL of reaction solvent A. -1 ~4 mL min -1 The ratio of the oxidizing gas flow is determined, and the oxidizing gas flow is introduced and reacted at 20℃~150℃ for 2 h~48 h; 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 organic cathode material.
[0010] Furthermore, the reaction solvent A is methanol, ethanol, isopropanol, n-butanol, or N,N-dimethylformamide.
[0011] Furthermore, the oxidizing gas flow is an oxygen flow or an air flow.
[0012] This invention also provides another method for preparing the polyquinone amine organic cathode material, which includes the following steps: dissolving 2,5-dichloro-1,4-benzoquinone and 1,2-cyclohexanediamine in reaction solvent B and carrying out a condensation reaction under inert gas protection; 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 polyquinone amine organic cathode material.
[0013] Furthermore, the method specifically includes the following steps: 2,5-dichloro-1,4-benzoquinone and 1.2-2.4-grams of 1,2-cyclohexanediamine are dissolved in 10-200 mL of reaction solvent B at a ratio of 1 gram of 2,5-dichloro-1,4-benzoquinone to 1.2-2.4-grams of 1,2-cyclohexanediamine. The mixture is then reacted at 20°C-150°C for 1-48 hours under an inert gas atmosphere. 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 organic cathode material.
[0014] Furthermore, the reaction solvent B is methanol, ethanol, isopropanol, n-butanol, or N,N-dimethylformamide.
[0015] Furthermore, the washing solvent is one or more of methanol, ethanol, isopropanol, n-butanol, N,N-dimethylformamide, and water.
[0016] This invention also provides the application of the polyquinone amine organic cathode material as described above in the field of ion batteries.
[0017] Compared with the prior art, the technical solution provided by the present invention has at least the following advantages:
[0018] This invention provides a polyquinone amine organic cathode material and its preparation method. This polyquinone amine organic cathode material has a specific microstructure, allowing for more stable intercalation of multivalent ions, and is poorly soluble in electrolytes, effectively suppressing the loss of active materials. Furthermore, the polyquinone amine organic cathode material can be prepared by two methods: Method 1: using 1,4-benzoquinone and 1,2-cyclohexanediamine as reactants dissolved in a reaction solvent, and performing an oxidative addition reaction; Method 2: using 2,5-dichloro-1,4-benzoquinone and 1,2-cyclohexanediamine as reactants dissolved in a reaction solvent, and performing a condensation reaction under inert gas protection. Both preparation methods are simple and feasible. Experiments have shown that when this polyquinone amine organic cathode material is applied in zinc-ion batteries, it exhibits good cycle reversibility and rate performance at 0.02 A g. -1 The highest discharge specific capacity at current density can reach 138 mAh g. -1 After 200 charge-discharge cycles, the discharge specific capacity remained at 78 mAh g. -1 . Attached Figure Description
[0019] 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.
[0020] Figure 1 The X-ray diffraction pattern of the polyquinone amine organic cathode material prepared in Example 1 of this invention;
[0021] Figure 2 This is a scanning electron microscope image of the polyquinone amine organic cathode material prepared in Example 1 of the present invention;
[0022] Figure 3 The infrared spectrum of the polyquinone amine organic cathode material prepared in Example 1 of this invention;
[0023] Figure 4 Thermogravimetric spectrum of the polyquinone amine organic cathode material prepared in Example 1 of this invention;
[0024] Figure 5 This is a cyclic voltammetry curve of the polyquinone amine organic cathode material prepared in Example 1 of the present invention in a zinc-ion battery;
[0025] Figure 6 The polyquinone amine organic cathode material prepared in this embodiment is used in zinc-ion batteries at 0.02 A g. -1 0.05 Ag -1 0.1 A g -1 0.2 A g -1 0.5 A g -1 and 1 A g -1Rate performance at current density;
[0026] Figure 7 The polyquinone amine organic cathode material prepared in this embodiment is used in a zinc-ion battery at a concentration of 0.02 A g. -1 Long-cycle diagram of 200 charge-discharge cycles at current density. Detailed Implementation
[0027] 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.
[0028] This invention provides a polyquinone amine organic cathode material, the structural formula of which is:
[0029] Where n is a natural number greater than or equal to 1.
[0030] The present invention also provides a method for preparing the polyquinone amine organic cathode material, the method comprising the following steps: dissolving 1,4-benzoquinone and 1,2-cyclohexanediamine in reaction solvent A and carrying out an oxidative addition reaction; after the reaction is completed, filtration is performed to obtain a filter cake; the filter cake is washed with a washing solvent and then dried to obtain the polyquinone amine organic cathode material.
[0031] The synthetic route for this reaction is shown below:
[0032]
[0033] Furthermore, the method specifically includes the following steps: 1,4-benzoquinone and 1,2-cyclohexanediamine are dissolved in reaction solvent A at a ratio of 10 mL to 200 mL per gram of 1,4-benzoquinone to 0.3 g to 1.3 g of 1,2-cyclohexanediamine; 0 mL of 1,4-benzoquinone and 1,2-cyclohexanediamine are bubbled into reaction solvent A at a ratio of 0 min per mL of reaction solvent A. -1 ~4 mL min -1 The ratio of the oxidizing gas flow is determined, and the oxidizing gas flow is introduced and reacted at 20℃~150℃ for 2 h~48 h; 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 organic cathode material.
[0034] Furthermore, the reaction solvent A is methanol, ethanol, isopropanol, n-butanol, or N,N-dimethylformamide.
[0035] Furthermore, the oxidizing gas flow is an oxygen flow or an air flow.
[0036] This invention also provides another method for preparing the polyquinone amine organic cathode material, the method comprising the following steps: dissolving 2,5-dichloro-1,4-benzoquinone and 1,2-cyclohexanediamine in reaction solvent B, and carrying out a condensation reaction under inert gas protection; after the reaction is completed, performing vacuum filtration to obtain a filter cake; washing the filter cake with a washing solvent and drying it to obtain the polyquinone amine organic cathode material.
[0037] The synthetic route for this reaction is shown below:
[0038]
[0039] Furthermore, the method specifically includes the following steps: 2,5-dichloro-1,4-benzoquinone and 1.2-2.4-grams of 1,2-cyclohexanediamine are dissolved in 10-200 mL of reaction solvent B at a ratio of 1 gram of 2,5-dichloro-1,4-benzoquinone to 1.2-2.4-grams of 1,2-cyclohexanediamine. The mixture is then reacted at 20°C-150°C for 1-48 hours under an inert gas atmosphere. 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 organic cathode material.
[0040] Furthermore, the reaction solvent B is methanol, ethanol, isopropanol, n-butanol, or N,N-dimethylformamide.
[0041] Furthermore, the inert gas is nitrogen, helium, or argon.
[0042] Furthermore, the washing solvent is one or more of methanol, ethanol, isopropanol, n-butanol, N,N-dimethylformamide, and water.
[0043] This invention also provides the application of the polyquinone amine organic cathode material as described above in the field of ion batteries.
[0044] The present invention will now be described in detail with reference to specific embodiments.
[0045] Example 1
[0046] 0.302 g (i.e. 2.86 mmol) of 1,4-benzoquinone and 0.184 g (i.e. 1.61 mmol) of 1,2-cyclohexanediamine were dissolved in 25 mL of N,N-dimethylformamide and reacted at 78 °C for 24 h. 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 water and then dried to obtain a black solid powder, which is the polyquinone amine organic cathode material of the present invention.
[0047] Figure 1The image shows the X-ray diffraction pattern of the polyquinone amine organic cathode material prepared in this embodiment. The main diffraction peak is a broad peak at 23º, indicating that the polyquinone amine organic cathode material in this invention is amorphous.
[0048] Figure 2 The image shows a scanning electron microscope (SEM) image of the polyquinone amine organic cathode material prepared in this embodiment, which appears as irregular particles at the micrometer scale.
[0049] Figure 3 The image shows the infrared spectrum of the polyquinone amine organic cathode material prepared in this embodiment. The main absorption peak range is around 1075 cm⁻¹. -1 1228 cm -1 1450 cm -1 1625 cm -1 2900 cm -1 2987 cm -1 and 3230 cm -1 ~3355cm -1 .
[0050] Figure 4 The thermogravimetric spectrum of the polyquinone amine organic cathode material prepared in this embodiment is shown, with a heating rate of 10 °C / min. -1 The figure shows that the weight loss is 3.7% in the range of 30℃ to 130℃, 17.88% in the range of 130℃ to 280℃, and significant weight loss occurs after 280℃.
[0051] The polyquinone amine organic cathode material prepared in this embodiment was used as the active material for the positive electrode of a zinc-ion battery. The organic 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.
[0052] Figure 5 The polyquinone amine organic cathode material prepared in Example 1 of this invention is used in zinc-ion batteries at 0.1 mV s. -1 0.2 mV s -1 0.3 mV s -1 0.4 mV s -1 0.5 mV s -1 0.6 mV s -1 0.8 mV s -1 and 1 mV s -1Cyclic voltammetry curves at different scan rates. The main oxidation peak is located around 0.7 V, and the main reduction peak is located around 0.5 V.
[0053] Figure 6 The polyquinone amine organic cathode material prepared in this embodiment is used in zinc-ion batteries at 0.02 A g. -1 0.05 Ag -1 0.1 A g -1 0.2 A g -1 0.5 A g -1 and 1 A g -1 Rate performance at current density, at 0.02 A g -1 The initial discharge specific capacity at current density is 148 mAh g. -1 .
[0054] Figure 7 The polyquinone amine organic cathode material prepared in this embodiment is used in a zinc-ion battery at a concentration of 0.02 A g. -1 The long-cycle graph at current density shows that the capacity retention rate is 53% after 200 charge-discharge cycles.
[0055] The electrochemical performance, including discharge specific capacity, rate performance stability, and long-cycle capacity retention, obtained from the above tests, is superior to existing cathode materials such as poly(1,4-benzoquinone-4,4'-diaminobiphenyl) and poly(1,4-benzoquinone-ethylenediamine). For example, compared to poly(1,4-benzoquinone-ethylenediamine) cathode material at 0.02 A g... -1 The discharge specific capacity of the first cycle at the current density is 102 mAh g. -1 The polyquinone amine organic cathode material of the present invention has significant performance advantages.
[0056] Example 2
[0057] 0.324 g (3 mmol) of 1,4-benzoquinone and 0.421 g (3.6 mmol) of 1,2-cyclohexanediamine were dissolved in 60 mL of methanol, and 20 mL of the solution was bubbled through the methanol. -1 An oxidizing gas stream was introduced and reacted at 30°C for 48 h. 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 ethanol and then dried to obtain a black solid powder, which is the polyquinone amine organic cathode material of the present invention.
[0058] Example 3
[0059] 0.324 g (3 mmol) of 1,4-benzoquinone and 0.389 g (3.6 mmol) of 1,2-cyclohexanediamine were dissolved in 10 mL of N,N-dimethylformamide, and 40 mL of the solution was bubbled through.-1 An oxidizing gas stream was introduced and reacted at 120°C for 2 hours. 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 water and then dried to obtain a black solid powder, which is the polyquinone amine organic cathode material of the present invention.
[0060] Example 4
[0061] 0.324 g (3 mmol) of 1,4-benzoquinone and 0.114 g (1 mmol) of 1,2-cyclohexanediamine were dissolved in 50 mL of isopropanol and reacted at 80 °C for 24 h. 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 then dried to obtain a black solid powder, which is the polyquinone amine organic cathode material of the present invention.
[0062] Example 5
[0063] 0.176 g (i.e. 1 mmol) of 2,5-dichloro-1,4-benzoquinone and 0.125 g (i.e. 1.1 mmol) of 1,2-cyclohexanediamine were dissolved in 20 mL of ethanol and reacted at 110 °C for 12 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 ethanol and N,N-dimethylformamide and then dried to obtain a black solid powder, which is the polyquinone amine organic cathode material of the present invention.
[0064] Example 6
[0065] 0.176 g (i.e. 1 mmol) of 2,5-dichloro-1,4-benzoquinone and 0.352 g (i.e. 0.3 mmol) of 1,2-cyclohexanediamine were dissolved in 10 mL of N,N-dimethylformamide and reacted at 140 °C for 12 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 organic cathode material of the present invention.
[0066] 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 organic cathode material, characterized in that, The structural formula of the polyquinone amine organic cathode material is as follows: ; where n is a natural number greater than 1.
2. The method for preparing the polyquinone amine organic cathode material according to claim 1, characterized in that, The method includes the following steps: 1,4-Benzoquinone and 1,2-cyclohexanediamine were dissolved in reaction solvent A and subjected to an oxidative addition 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 organic cathode material.
3. The method for preparing the polyquinone amine organic cathode material according to claim 2, characterized in that, The method specifically includes the following steps: According to the ratio of 1 gram of 1,4-benzoquinone to 0.3 to 1.3 grams of 1,2-cyclohexanediamine dissolved in 10 to 200 mL of reaction solvent A, 1,4-benzoquinone and 1,2-cyclohexanediamine were dissolved in reaction solvent A; 1 / 3 mL of the solution was bubbled into each mL of reaction solvent A. -1 ~4 mL min -1 The ratio of the oxidizing gas flow is determined, and the oxidizing gas flow is introduced and reacted at 200℃~1500℃ for 2 h~48 h; 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 organic cathode material.
4. The method for preparing the polyquinone amine organic cathode material according to claim 3, characterized in that, The reaction solvent A is methanol, ethanol, isopropanol, n-butanol, or N,N-dimethylformamide.
5. The method for preparing the polyquinone amine organic cathode material according to claim 3, characterized in that, The oxidizing gas flow is an oxygen flow or an air flow.
6. The method for preparing the polyquinone amine organic cathode material according to claim 1, characterized in that, The method includes the following steps: 2,5-Dichloro-1,4-benzoquinone and 1,2-cyclohexanediamine were dissolved in reaction solvent B and subjected to a condensation reaction under inert gas protection. 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 organic cathode material.
7. The method for preparing the polyquinone amine organic cathode material according to claim 6, characterized in that, The method specifically includes the following steps: According to the ratio of 1.2 g to 2.4 g of 1,2-cyclohexanediamine dissolved in 10 mL to 200 mL of reaction solvent B, 2,5-dichloro-1,4-benzoquinone and 1,2-cyclohexanediamine were dissolved in reaction solvent B and reacted at 20 °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 organic cathode material.
8. The method for preparing the polyquinone amine organic cathode material according to claim 7, characterized in that, The reaction solvent B is methanol, ethanol, isopropanol, n-butanol, or N,N-dimethylformamide.
9. The method for preparing the polyquinone amine organic cathode material according to claim 3 or 7, characterized in that, The washing solvent is one or more of methanol, ethanol, isopropanol, n-butanol, N,N-dimethylformamide, and water.
10. The application of the polyquinone amine organic cathode material as described in claim 1 in the field of ion batteries.