A polyquinone urea organic positive electrode material and a preparation method and application thereof
By preparing polyquinone urea organic cathode material, the problems of poor specific capacity utilization and long cycle performance in multivalent ion batteries were solved, and the performance of zinc-ion batteries was improved by achieving high efficiency.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- YANSHAN UNIV
- Filing Date
- 2023-09-05
- Publication Date
- 2026-05-19
AI Technical Summary
Existing organic cathode materials do not perform well in multivalent ion batteries in terms of specific capacity utilization, rate capability, and long cycle life, making it difficult to meet the application requirements of multivalent ion batteries.
A method for preparing polyquinone urea organic cathode material was adopted, in which 2,3,4,6-tetrachlorobenzoquinone and urea were heated and condensed under inert gas protection to prepare a polyquinone urea organic cathode material with a specific structure for use in zinc-ion batteries.
Polyquinone urea organic cathode material exhibits stable multivalent ion intercalation capability in zinc-ion batteries, suppresses active material loss, has high initial discharge specific capacity, excellent long-term cycle performance, and high capacity retention after 1000 charge-discharge cycles.
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Figure CN117143333B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of battery technology, specifically to a polyquinone urea organic 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 and sodium-ion batteries; however, the number of organic cathode material structures suitable for multivalent ion batteries is relatively small. In multivalent ion batteries, the electrochemical performance of organic cathode materials, such as specific capacity utilization, rate capability, and long-cycle performance, is not ideal. 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 urea organic 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 urea 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 urea organic cathode material, the method comprising the following steps: dissolving 2,3,4,6-tetrachlorobenzoquinone and urea 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 polyquinone urea organic cathode material.
[0009] Furthermore, the method specifically includes the following steps: 2,3,4,6-tetrachlorobenzoquinone and 0.2 to 1.0 grams of urea are dissolved in 5 to 200 mL of reaction solvent at a ratio of 1 gram of 2,3,4,6-tetrachlorobenzoquinone to 0.2 to 1.0 grams of urea in 5 mL to 200 mL of reaction solvent. The mixture is reacted at 50°C to 150°C for 1 to 48 hours 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 urea organic cathode material.
[0010] Furthermore, the reaction solvent is methanol, ethanol, isopropanol, n-butanol, pyridine, or N,N-dimethylformamide.
[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 urea organic cathode material as 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 urea organic cathode material, its preparation method, and its applications. This polyquinone urea organic 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 the raw materials are inexpensive. Experiments have shown that when this polyquinone urea organic cathode material is applied in zinc-ion batteries, it achieves optimal performance at 0.02 Ag. -1 The first-cycle discharge specific capacity can reach 154 mAh g at the current density. -1 In 0.1Ag -1 The initial discharge specific capacity remains at 65 mAh g at the current density. -1 The capacity retention rate is 57% after 1000 charge-discharge cycles. 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 urea organic cathode material prepared in Example 1 of this invention;
[0018] Figure 2 This is a scanning electron microscope image of the polyquinone urea organic cathode material prepared in Example 1 of the present invention;
[0019] Figure 3 The infrared spectrum of the polyquinone urea organic cathode material prepared in Example 1 of this invention;
[0020] Figure 4 The X-ray photoelectron spectrum of the polyquinone urea organic cathode material prepared in Example 1 of this invention is shown below.
[0021] Figure 5 Thermogravimetric spectrum of the polyquinone urea organic cathode material prepared in Example 1 of this invention;
[0022] Figure 6 This is a cyclic voltammetry curve of the polyquinone urea organic cathode material prepared in Example 1 of the present invention in a zinc-ion battery;
[0023] Figure 7 The polyquinone urea organic 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;
[0024] Figure 8 The polyquinone urea organic cathode material prepared in Example 1 of this invention was used in a zinc-ion battery at a concentration of 0.1 Ag. -1 Long-cycle diagram of 1000 charge-discharge cycles at current density. Detailed Implementation
[0025] 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.
[0026] This invention provides an organic cathode material, the structural formula of which is:
[0027] Where n is a natural number greater than or equal to 1.
[0028] 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 urea in a reaction solvent, and heating under inert gas protection to carry out a condensation reaction; 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 urea organic cathode material.
[0029] The synthetic route for this reaction is shown below:
[0030]
[0031] Furthermore, the method specifically includes the following steps: 2,3,4,6-tetrachlorobenzoquinone and 0.2 to 1.0 grams of urea are dissolved in 5 to 200 mL of reaction solvent at a ratio of 1 gram of 2,3,4,6-tetrachlorobenzoquinone to 0.2 to 1.0 grams of urea in 5 mL to 200 mL of reaction solvent. The mixture is reacted at 50°C to 150°C for 1 to 48 hours 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 urea organic cathode material.
[0032] Furthermore, the reaction solvent is methanol, ethanol, isopropanol, n-butanol, pyridine, or N,N-dimethylformamide.
[0033] Furthermore, the inert gas is nitrogen, helium, or argon.
[0034] Furthermore, the washing solvent is one or more of methanol, ethanol, isopropanol, n-butanol, N,N-dimethylformamide, and water.
[0035] This invention also provides the application of the organic cathode material described above in the field of ion batteries.
[0036] The present invention will now be described in detail with reference to specific embodiments.
[0037] Example 1
[0038] 0.246 g (i.e., 1 mmol) of 2,3,4,6-tetrachlorobenzoquinone and 0.121 g (i.e., 2 mmol) of urea were dissolved in 20 mL of N,N-dimethylformamide and reacted at 150 °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 ethanol and water and then dried to obtain a black solid powder, which is the polyquinone urea organic cathode material of the present invention.
[0039] Figure 1 The image shows the X-ray diffraction pattern of the polyquinone urea organic cathode material prepared in this embodiment. The main diffraction peak is a broad peak at 27°, indicating that the polyquinone urea organic cathode material in the invention is amorphous.
[0040] Figure 2 The image shows a scanning electron microscope (SEM) image of the polyquinone urea organic cathode material prepared in this embodiment, which appears as clump-like particles at the micrometer scale.
[0041] Figure 3 The image shows the infrared spectrum of the polyquinone urea organic cathode material prepared in this embodiment. The main absorption peak range is around 892 cm⁻¹.-1 1065cm -1 1250cm -1 1555cm -1 1800cm -1 2900cm -1 2970cm -1 and 3150cm -1 ~3380cm -1 .
[0042] Figure 4 The image shows the X-ray photoelectron spectrum of the polyquinone urea organic cathode material prepared in this embodiment. The main peaks in the image are at 200 eV, 285 eV, 399 eV and 531 eV, which correspond to the electron binding energies of Cl2p, C1s, N1s and O1s, respectively.
[0043] Figure 5 The thermogravimetric spectrum of the organic cathode material prepared in this embodiment shows a small amount of mass loss at around 100°C and a large amount of mass loss after 300°C.
[0044] The polyquinone urea organic 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.
[0045] Figure 6 The polyquinone urea organic cathode material prepared in Example 1 of this invention is used in zinc-ion batteries at 0.1 mV s. -1 0.2mV s -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 the specified scan rate. The scan voltage range is 0.3V to 1.8V. The oxidation peak is located at approximately 0.95V, and the reduction peak is located at approximately 0.75V.
[0046] Figure 7 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 initial discharge specific capacity is 154 mAh g. -1 The current density increased to 1.0 Ag. -1 The discharge capacity decreased to 27 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 81 mAh g. -1 .
[0047] Figure 8 The organic cathode material prepared in this embodiment is used in a zinc-ion battery at a concentration of 0.1 Ag. -1 Long-cycle graph at current density, first-cycle discharge specific capacity is 65mAh g. -1 After 1000 charge-discharge cycles, the capacity retention rate was 57%.
[0048] 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 organic cathode materials such as poly(1,4-benzoquinone-ethylenediamine) and poly(1,4-benzoquinone-urea).
[0049] Example 2
[0050] 0.246 g (i.e., 1 mmol) of 2,3,4,6-tetrachlorobenzoquinone and 0.049 g (i.e., 0.8 mmol) of urea were dissolved in 10 mL of methanol and reacted at 60 °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 N,N-dimethylformamide and water and then dried to obtain a black solid powder, which is the polyquinone urea organic cathode material of the present invention.
[0051] Example 3
[0052] 0.246 g (i.e., 1 mmol) of 2,3,4,6-tetrachlorobenzoquinone and 0.061 g (i.e., 1 mmol) of urea were dissolved in 50 mL of ethanol and reacted at 75 °C for 24 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 N,N-dimethylformamide and then dried to obtain a black solid powder, which is the polyquinone urea organic cathode material of the present invention.
[0053] Example 4
[0054] 0.246 g (i.e., 1 mmol) of 2,3,4,6-tetrachlorobenzoquinone and 0.090 g (i.e., 1.5 mmol) of urea were dissolved in 20 mL of N,N-dimethylformamide and reacted at 150 °C for 2 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 water and then dried to obtain a black solid powder, which is the polyquinone urea organic cathode material of the present invention.
[0055] Example 5
[0056] 0.246 g (i.e., 1 mmol) of 2,3,4,6-tetrachlorobenzoquinone and 0.090 g (i.e., 1.5 mmol) of urea were dissolved in 50 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 n-butanol and water and then dried to obtain a black solid powder, which is the polyquinone urea organic cathode material of the present invention.
[0057] Example 6
[0058] 0.246 g (i.e., 1 mmol) of 2,3,4,6-tetrachlorobenzoquinone and 0.121 g (i.e., 2 mmol) of urea were dissolved in 50 mL of n-butanol and reacted at 110 °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 urea organic cathode material of the present invention.
[0059] 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 urea organic cathode material, characterized in that, The structural formula of the polyquinone urea organic cathode material is: Where n is a natural number greater than 1.
2. The method for preparing the polyquinone urea organic cathode material according to claim 1, characterized in that, The method includes the following steps: 2,3,4,6-Tetrachlorobenzoquinone and urea 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 urea organic cathode material.
3. The method for preparing the polyquinone urea organic cathode material according to claim 2, characterized in that, The method specifically includes the following steps: According to the ratio of 0.2 g to 1.0 g of urea dissolved in 5 mL to 200 mL of reaction solvent, 2,3,4,6-tetrachlorobenzoquinone and urea were dissolved in the reaction solvent and reacted at 50 °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 urea organic cathode material.
4. The method for preparing the polyquinone urea organic cathode material according to claim 3, characterized in that, The reaction solvent is methanol, ethanol, isopropanol, n-butanol, pyridine, or N,N-dimethylformamide.
5. The method for preparing the polyquinone urea organic cathode material according to claim 3, characterized in that, The inert gas is nitrogen, helium, or argon.
6. The method for preparing the polyquinone urea organic 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 urea organic cathode material as described in claim 1 in the field of ion batteries.