A layered bis(tetraaminobenzoquinone) organic electrode material, preparation method and application thereof

Abstract

The present invention belongs to the field of new chemical power sources and relates to a layered bi-tetraaminobenzoquinone organic electrode material and its preparation method and application. The chemical formula of the material is C 12 H8N6O4 has a highly ordered layered structure with an interlayer spacing of 0.02-0.03μm, and has terminal amino groups, p-benzoquinone and pyrazine. The preparation method is to dissolve tetraamino-p-benzoquinone and a soft template in an organic solvent to form a uniform mixed solution, heat it to 100-150°C and react for 12-24 hours, cool it, wash the solid, and filter it to obtain a layered bis-tetraamino-p-benzoquinone organic electrode material. This material can be used in a variety of ion battery systems including lithium ions, sodium ions, and zinc ions. The present invention achieves a high degree of ordering of the crystal structure and full exposure of the active sites of the functional groups through morphology control technology, significantly improving the cycle stability and reversible specific capacity, and the mass energy density is superior to that of traditional inorganic positive electrode materials.

Description

Technical Field

[0001] The invention belongs to the field of novel chemical power sources and relates to a layered bis-tetraaminobenzoquinone organic electrode material, a preparation method and an application thereof. Background Art

[0002] In recent years, organic electrode materials have attracted widespread attention due to their lightweight, sustainable raw material, cost-effectiveness, environmental compatibility, flexibility, and the potential for performance optimization through molecular engineering. The structural designability of these materials offers the potential for developing high-performance batteries with high specific capacity and controllable discharge platforms. However, limitations in the electron delocalization capabilities and solubility issues of organic electrode materials severely restrict their rate performance and cycling stability in lithium-ion batteries and other alkali metal ion batteries. Summary of the Invention

[0003] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a layered bis(tetraaminobenzoquinone) organic electrode material and its preparation method and application, which solves the problems of limited electron delocalization ability and solubility of traditional organic electrode materials.

[0004] The technical solution of the present invention:

[0005] The first aspect of the present invention is to provide a layered bis-tetraaminobenzoquinone organic electrode material, referred to as bTABQ, with a chemical formula of C 12 H8N6O4 has a highly ordered layered structure with an interlayer spacing of 0.02 - 0.03 μm. Its molecular structure is as follows:

[0006] .

[0007] Its molecular structure has terminal amino groups, p-benzoquinone and pyrazine, and is a product with a layered structure after morphology control. The molecule has a capacity of 535.70 mAh·g -1 The bTABQ molecule exhibits a high theoretical specific capacity. The presence of p-π conjugated and π-π conjugated networks within the p-benzoquinone extended pyrazine skeleton endows it with excellent electronic conductivity. Furthermore, the intra- and intermolecular hydrogen bond networks, formed by carbonyl (-C=O) and amino (-NH2) groups, significantly enhance the material's solubility resistance and structural stability in organic solvents, which are crucial for improving the cycle life and electrochemical stability of electrode materials.

[0008] The second aspect of the present invention provides a method for preparing a layered bis-tetraaminobenzoquinone organic electrode material. Tetraaminobenzoquinone and a soft template are dissolved in an organic solvent, stirred, mixed, and ultrasonically treated to form a uniform mixed solution. The mixed solution is then transferred to a sealed reactor and heated at a reaction temperature of 100-150°C for 12-24 hours. After the reaction system temperature cools to room temperature, the product is washed with an organic solvent and filtered to obtain the layered bis-tetraaminobenzoquinone (bTABQ) material.

[0009] The present invention introduces a soft template to control the material's morphology. Under heating conditions, TABQ molecules undergo a self-coupling reaction to form bTABQ. Subsequently, the bTABQ molecules assemble in an orderly manner within the oriented spatial network formed by the soft template, forming a layered structure. This process significantly increases the material's specific surface area and increases the exposure of active functional groups, thereby enhancing the electrochemical performance of the electrode material. The synthesized layered bTABQ material can deliver 460 mAh·g –1 The specific capacity is higher than that of various existing inorganic materials, providing a new solution for the design and synthesis of organic positive electrode materials.

[0010] Furthermore, the mass ratio of the tetraaminobenzoquinone to the soft template is 0.6-0.7:5.0-6.0.

[0011] More preferably, the reaction temperature is 120-130° C., and the reaction time is 12-15 hours.

[0012] Furthermore, the soft template includes but is not limited to tetrabutylammonium chloride (TBACl), tetraethylammonium chloride (TEACl) and tetramethylammonium chloride (TMACl) surfactants; preferably, the soft template is tetrabutylammonium chloride, and the purity of tetrabutylammonium chloride is 85%.

[0013] Furthermore, the organic solvent includes but is not limited to N, N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc) and methanol.

[0014] The third aspect of the present invention provides an application of the layered bis(tetraaminobenzoquinone) organic electrode material in lithium ion batteries, sodium ion batteries, and zinc ion batteries.

[0015] Layered bis(tetraaminobenzoquinone) organic electrode material, conductive carbon black and binder are mixed in a mass ratio of 6:3:1 to form an electrode slurry, which is then coated on a current collector and dried to form a positive electrode sheet.

[0016] When the positive electrode plate is used in a lithium-ion battery, the negative electrode adopts metallic lithium and the electrolyte adopts a lithium salt ether solution.

[0017] When the positive electrode plate is used in a sodium ion battery, the negative electrode adopts metallic sodium and the electrolyte adopts a sodium salt ether solution.

[0018] When the positive electrode plate is used in a zinc ion battery, the negative electrode is made of metallic zinc and the electrolyte is a zinc salt aqueous solution.

[0019] This paper focuses on the preparation of a layered bis-tetraaminobenzoquinone (bTABQ) and its application as a positive electrode material for lithium-ion batteries. During the material preparation process, the amount of soft template added, the heating temperature, and the stirring time can be adjusted according to actual conditions.

[0020] Advantages and beneficial effects of the present invention:

[0021] 1. Highly Ordered Layered Structure: A highly ordered layered bTABQ material was successfully prepared by using a soft template for morphology-induced synthesis. This structure maintains the structural stability of the electrode material during charge and discharge, significantly improving its cycling stability. Furthermore, the highly ordered layered structure increases the material's specific surface area, thereby expanding the effective contact area between the electrode material and the electrolyte, improving the utilization of active sites, and ultimately increasing the energy density of the electrode material.

[0022] 2. High crystallinity and exposure of active functional groups: The layered bTABQ materials synthesized by morphology induction show excellent crystallinity, such as Figure 9 As shown in Figure 2, the sharpness of the (102) diffraction characteristic peak is significantly improved compared with the original bTABQ without morphology control, which indicates that the crystallinity of the material has been significantly enhanced. This high crystallinity characteristic helps to fully expose the active functional groups, such as Figure 10 As shown in the figure, under the same test conditions, the intensity of the infrared spectroscopy (ATR-IR) absorbance signal of the layered bTABQ is higher, indicating that the exposure of the active functional groups has been improved. This enhanced exposure of the active sites is conducive to promoting the transport efficiency of ions and electrons, thereby significantly improving the overall electrochemical performance of the material.

[0023] 3. Improved specific capacity and cycle stability: The layered bTABQ organic cathode material designed in this invention exhibits excellent electronic conductivity thanks to the p-π conjugated and π-π conjugated networks in its p-benzoquinone extended pyrazine skeleton. In addition, the hydrogen bond network formed within and between bTABQ molecules significantly enhances the material's resistance to dissolution in organic solvents, which is extremely important for maintaining the structural stability of the electrode material and improving its cycle life. The presence of the hydrogen bond network also improves the material's mechanical stability, reducing structural damage caused by volume changes during charge and discharge, thereby extending the service life of the electrode material.

[0024] 4. Through rational molecular design and simple synthetic steps, this invention successfully prepared an organic cathode material with a highly ordered layered structure, high crystallinity, high specific capacity, and excellent cycling stability. This material is expected to be used in new, high-performance, environmentally friendly, high-specific-capacity batteries.

[0025] 5. The layered bTABQ material provided by the present invention achieves a highly ordered crystal structure and fully exposed functional group active sites through morphology control technology, significantly improving the cycle stability and reversible specific capacity (460 mAh g -1 ), and its mass energy density is better than that of traditional inorganic cathode materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 This is an SEM image of the layered bTABQ prepared in Example 1;

[0027] Figure 2 for Figure 1 A partial enlarged view of

[0028] Figure 3 SEM image of the original bTABQ;

[0029] Figure 4 for Figure 3 A partial enlarged view of

[0030] Figure 5 This is the SEM image of the bTABQ block in comparative example 1;

[0031] Figure 6 for Figure 5 A partial enlarged view of

[0032] Figure 7 is the SEM image of the layered bTABQ (large) of comparative example 2;

[0033] Figure 8 for Figure 7 A partial enlarged view of

[0034] Figure 9 XRD comparison diagram of layered bTABQ and pristine bTABQ in Example 1;

[0035] Figure 10 IR comparison chart of layered bTABQ and pristine bTABQ in Example 1;

[0036] Figure 11 This is a Raman comparison chart of layered bTABQ and pristine bTABQ in Example 1;

[0037] Figure 12 Example 1: Layered bTABQ for lithium-ion batteries at 0.1 A·g -1Charge and discharge cycle curves under current density;

[0038] Figure 13 For the original bTABQ used in lithium-ion batteries at 0.1 A·g -1 Charge and discharge cycle curves under current density;

[0039] Figure 14 Comparative Example 1: The bulk bTABQ is used in lithium-ion batteries at 0.1 A·g -1 Charge and discharge cycle curves under current density;

[0040] Figure 15 Comparative Example 2: Layered bTABQ (large) for lithium-ion batteries at 0.1 A·g -1 Charge and discharge cycle curves under current density;

[0041] Figure 16 Example 1: Layered bTABQ for sodium ion batteries at 0.1 A·g -1 Charge and discharge cycle curves under current density;

[0042] Figure 17 Example 1: Layered bTABQ used in zinc ion batteries at 0.1 A·g -1 Charge and discharge cycle curves at different current densities. DETAILED DESCRIPTION

[0043] The present invention will be further described in detail below through specific examples. The following examples are only illustrative and not restrictive, and the scope of protection of the present invention cannot be limited thereto.

[0044] Example 1

[0045] A method for preparing a layered b-TABQ organic electrode material comprises dissolving 0.6726 g of TABQ and 5.5584 g of TBACl (85% purity) in 40-50 mL of DMF, stirring and mixing, and ultrasonicating to form a uniform mixed solution. The mixed solution is then transferred to a closed reactor and reacted at 125°C for 12 hours. After the reaction is completed, the reaction system temperature is cooled to room temperature, and the product is washed with DMF and methanol, filtered several times, and dried to obtain a layered bTABQ organic electrode material.

[0046] Comparative Example 1

[0047] The difference from Example 1 is that TBACl (purity 100%) is used to obtain bulk bTABQ.

[0048] Comparative Example 2

[0049] The difference from Example 1 is that TBACl is replaced with TBABr (purity 98%) to obtain layered bTABQ (large).

[0050] Figures 1-8 The following are scanning electron microscope (SEM) images of bTABQ synthesized in Example 1, Comparative Example 1, Comparative Example 2, and in the original state. From the image results, it can be seen that there are significant differences in the microstructural characteristics of different samples. The layered bTABQ is in the form of uniform small particles and has a highly ordered layered structure with an interlayer spacing in the range of 0.02-0.03 μm; the original bTABQ presents a cluster structure; the bulk bTABQ is also composed of uniform small particles, but there is no layered structure; and the layered bTABQ (large) has a larger and more uniformly distributed particle size and also has a layered structure with an interlayer spacing of 0.04-0.05 μm.

[0051] Figures 9-11 The crystallization characteristics and functional group exposure differences between the layered bTABQ in Example 1 and the original bTABQ were compared by X-ray diffraction (XRD), infrared spectroscopy (IR) and Raman spectroscopy, which showed that:

[0052] XRD analysis shows that the diffraction peak intensity of the layered bTABQ at the 102 crystal plane (corresponding to a Bragg angle 2θ≈28.2°) is significantly higher than that of the pristine sample, and the peak shape is sharper. This indicates that the introduction of the layered structure significantly improves the crystalline order of the material, which may be related to its highly regular interlayer spacing (0.02-0.03 μm).

[0053] Infrared spectroscopy (IR) characteristics: The absorption peak intensity of key functional groups (such as C=O, NH, etc.) in the IR spectrum of layered bTABQ is significantly enhanced and the peak width is narrowed. This feature indicates that the formation of the layered structure promotes the effective exposure of active functional groups.

[0054] Raman spectroscopy characterization: The layered bTABQ exhibits higher Raman peak intensity and a smaller half-width (FWHM), reflecting the improved symmetry of the chemical bond vibrational modes within the material. Combined with XRD results, it can be inferred that the layered structure optimizes the order of molecular arrangement and reduces the proportion of amorphous or disordered regions. Furthermore, the enhanced Raman peak intensity may indicate stronger electron-phonon coupling.

[0055] Application Example 1:

[0056] bTABQ from Example 1, Comparative Example 1, Comparative Example 2, or pristine state was mixed with conductive carbon black (Super-p) and a binder (polyvinylidene fluoride, PVDF) in a mass ratio of 6:3:1 and ground. The resulting homogeneous mixture was then mixed with an appropriate amount of N-methylpyrrolidone (NMP) to form a uniform electrode slurry. This electrode slurry was evenly coated onto an aluminum foil current collector using a doctor blade process, with the coating thickness precisely controlled to 250-500 microns to ensure uniformity and consistency across the electrode sheet. The coated aluminum foil current collector was dried in a vacuum oven at 105-110°C for 12 hours to remove the solvent and solidify the electrode material. After drying, the electrode sheet was cut into circular positive electrode sheets with a diameter of 12 mm for battery testing.

[0057] Application Example 2: Assembly of Lithium-ion Batteries

[0058] Button cell batteries are assembled in a glove box, and the environment must strictly control oxygen and moisture concentrations to no more than 0.01 ppm. The assembly process is carried out as follows: First, the positive electrode shell is placed on the operating table, and the positive electrode sheet prepared in Example 1 is placed as the positive electrode of the battery. Subsequently, a Celgard 2400 diaphragm is superimposed to separate the positive and negative electrodes to prevent short circuits, and an appropriate amount of electrolyte (1 M LiTFSI, the solvent is tetraethylene glycol dimethyl ether) is dripped onto the diaphragm to provide an ion transport medium for the battery. Next, the metal lithium sheet is placed on the diaphragm, and the gasket and spring are superimposed in sequence. Finally, the negative electrode shell is covered on the top layer and sealed using a battery packaging machine. The assembled battery is left to stand for its internal components to fully stabilize before the electrochemical performance test is carried out.

[0059] Application Example 3: Assembly of Sodium Ion Batteries

[0060] When assembling button cells in a glove box, it is necessary to ensure that the oxygen and water vapor concentrations in the operating environment are less than 0.01ppm. The assembly process is carried out as follows: First, place the negative electrode shell on the operating table, insert the spring and gasket into it in turn, and then place the metal sodium negative electrode on the gasket. Subsequently, a glass fiber separator is stacked directly above the sodium sheet to ensure that the negative electrode sheet is completely covered, and then the electrolyte (1M NaPF6, the solvent is diethylene glycol dimethyl ether‌) is dripped onto the separator. Next, the positive electrode sheet prepared in Example 1 is placed on the glass fiber separator. Finally, the positive electrode shell is covered on the top layer and sealed using a battery packaging machine. The assembled battery is left to stand to ensure that the components inside the battery are stable before performing an electrochemical performance test.

[0061] Application Example 4: Assembly of zinc ion batteries

[0062] The assembly of aqueous zinc ion button batteries can be carried out in an air environment, and the ambient air should be kept relatively clean and dry. The assembly process is as follows: First, place the negative electrode shell on the operating table, and then use tweezers to place the zinc foil negative electrode sheet in the negative electrode shell. Next, lay a layer of glass fiber diaphragm directly above the negative electrode sheet, and drip an appropriate amount of electrolyte (2MZnSO4 aqueous solution) on the diaphragm to ensure that it is fully infiltrated. Then, place the positive electrode sheet prepared in Example 1 flat on top of the glass fiber diaphragm, and stack a gasket and a shrapnel on it in turn. Finally, cover the positive electrode shell on the top layer and use a battery packaging machine to seal it. After assembly is completed, let the battery stand for a period of time to ensure that the components inside the battery are stable, and then the electrochemical performance test can be carried out.

[0063] Figure 12-15 The charge and discharge curves of batteries using layered bTABQ, pristine bTABQ, bulk bTABQ, and layered bTABQ (large) as cathode materials for lithium-ion batteries are presented. Figure 16 and Figure 17 The results show that layered bTABQ can be used as cathode materials for sodium-ion batteries and aqueous zinc-ion batteries at 0.1 A·g -1 Charge and discharge curves at different current densities.

[0064] In the electrochemical performance test of lithium-ion batteries, layered bTABQ showed excellent performance. -1 At a current density of 1.5 GHz, its discharge capacity is as high as 460 mAh·g -1 , has a clear discharge platform, and exhibits excellent cycling stability. In comparison, the discharge capacity of the original bTABQ at the same current density is about 325 mAh g -1 The voltage platform is relatively flat. The specific capacity of bulk bTABQ is significantly lower, about 250 mAh g -1 , not only the voltage platform is not obvious, but also the specific capacity decay phenomenon is prominent. Layered bTABQ (large) also has the problem of unclear voltage platform and poor cycling stability.

[0065] The layered bTABQ material involved in the present invention has the advantages of high specific capacity, long cycle life, low cost and easy preparation, and has good application prospects.

[0066] The above description is only a preferred embodiment of the present invention. It should be pointed out that a person skilled in the art can make several modifications and improvements without departing from the inventive concept, and these all fall within the scope of protection of the present invention.

Claims

1. A layered bis(tetraaminobenzoquinone) organic electrode material, characterized in that: The chemical formula of the material is C 12 H8N6O4 has a highly ordered layered structure with an interlayer spacing of 0.02 - 0.03 μm. Its molecular structure is as follows: The preparation method is as follows: tetraaminobenzoquinone and a soft template are dissolved in an organic solvent to form a uniform mixed solution, which is then heated to 100-150°C for reaction for 12-24 hours, cooled, the solid is washed, and filtered to obtain a layered bis-tetraaminobenzoquinone material. The soft template is tetrabutylammonium chloride, and the purity of the tetrabutylammonium chloride is 85%.

2. The layered bis(tetraaminobenzoquinone) organic electrode material according to claim 1, characterized in that: The mass ratio of the tetraaminobenzoquinone to the soft template is 0.6-0.7:5.0-6.

0.

3. The layered bis-tetraaminobenzoquinone organic electrode material according to claim 1, characterized in that: The organic solvent is one or more of N, N-dimethylformamide, N-methylpyrrolidone, N, N-dimethylacetamide, and methanol.

4. Use of the layered bis(tetraaminobenzoquinone) organic electrode material as claimed in claim 1 in lithium ion batteries, sodium ion batteries and zinc ion batteries.

5. The use according to claim 4, characterized in that Layered bis(tetraaminobenzoquinone) organic electrode material, conductive carbon black and binder are mixed in a mass ratio of 6:3:1 to form an electrode slurry, which is then coated on a current collector and dried to form a positive electrode sheet.

6. The use according to claim 5, characterized in that When the positive electrode plate is used in a lithium-ion battery, the negative electrode adopts metallic lithium and the electrolyte adopts a lithium salt ether solution.

7. The use according to claim 5, characterized in that When the positive electrode plate is used in a sodium ion battery, the negative electrode adopts metallic sodium and the electrolyte adopts a sodium salt ether solution.

8. The use according to claim 5, characterized in that When the positive electrode plate is used in a zinc ion battery, the negative electrode is made of metallic zinc and the electrolyte is a zinc salt aqueous solution.

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