Layered bis (tetraamino) p-benzoquinone organic electrode material and preparation method and application thereof

Abstract

The invention belongs to the field of novel chemical power sources, and relates to a layered bis-tetraamino p-benzoquinone organic electrode material and a preparation method and application thereof. The chemical formula of the material is C12H8N6O4, the material has a highly ordered layered structure, the interlayer spacing is 0.02-0.03 [mu] m, and the material has terminal amino, p-benzoquinone and pyrazine. The preparation method comprises the following steps: dissolving tetraamino p-benzoquinone and a soft template agent in an organic solvent to form a uniformly mixed solution, heating to 100-150 DEG C, reacting for 12-24 hours, cooling, washing a solid, and carrying out suction filtration to obtain the layered bis-tetraamino p-benzoquinone organic electrode material. The material can be applied to various ion battery systems including lithium ions, sodium ions and zinc ions. According to the invention, high ordering of a crystal structure and full exposure of active sites of functional groups are realized through a morphology regulation and control technology, the cycling stability and reversible specific capacity are remarkably improved, and the mass energy density is superior to that of a traditional inorganic positive electrode material.

Description

Technical Field

[0001] The present invention belongs to the field of new chemical power sources, and relates to a layered bis(tetraamino-p-benzoquinone) organic electrode material, its preparation method and application. Background Art

[0002] In recent years, organic electrode materials have received extensive attention due to their light weight, raw material sustainability, cost-effectiveness, environmental compatibility, flexibility, and the potential to optimize performance through molecular engineering. The structural designability of these materials provides the possibility to develop high-performance batteries with high specific capacity and controllable discharge platforms. However, the limitations in the electron delocalization ability and solubility problems of organic electrode materials severely restrict their rate performance and cycle 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(tetraamino-p-benzoquinone) organic electrode material, its preparation method and application, which solve 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 provides a layered bis(tetraamino-p-benzoquinone) organic electrode material, abbreviated as bTABQ, with the chemical formula C 12 H8N6O4, having a highly ordered layered structure with an interlayer spacing of 0.02 - 0.03 μm, and 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 regulation. The molecule has a high theoretical specific capacity of 535.70 mAh·g -1 . In the p-benzoquinone extended pyrazine skeleton of the bTABQ molecule, the presence of p-π conjugation and π-π conjugation networks endows it with excellent electronic conductivity. In addition, the intra- and intermolecular hydrogen bond networks formed by carbonyl groups (-C=O) and amino groups (-NH2) significantly improve the anti-solubility and structural stability of the material in organic solvents, which is crucial for enhancing the cycle life and electrochemical stability of the electrode material.

[0008] The second aspect of the present invention is to provide a method for preparing a layered double tetraamino-p-benzoquinone organic electrode material. Tetraamino-p-benzoquinone and a soft template agent are dissolved in an organic solvent, and after stirring and mixing and ultrasonic treatment, a uniformly mixed solution is formed. Subsequently, the mixed solution is transferred to a closed reactor and heated at a reaction temperature of 100 - 150 °C for 12 - 24 hours. After the reaction system temperature drops to room temperature, the product is washed with an organic solvent, and finally filtered by suction to obtain a layered double tetraamino-p-benzoquinone (bTABQ) material.

[0009] The present invention introduces a soft template agent to regulate the morphology of the material. Under heating conditions, TABQ molecules form bTABQ through self-coupling reaction. Subsequently, bTABQ molecules are orderly assembled in the directional space network composed of the soft template agent to form a layered structure. This process significantly increases the specific surface area of the material and the exposure degree of active functional groups, thereby enhancing the electrochemical performance of the electrode material. The synthesized layered bTABQ material can exhibit a specific capacity of 460 mAh·g –1 , which is higher than various existing inorganic materials, providing a new scheme for the design and synthesis of organic cathode materials.

[0010] Further, the mass ratio of the tetraamino-p-benzoquinone to the soft template agent is 0.6 - 0.7:5.0 - 6.0.

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

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

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

[0014] The third aspect of the present invention is to provide an application of the described layered double tetraamino-p-benzoquinone organic electrode material in lithium-ion batteries, sodium-ion batteries, and zinc-ion batteries.

[0015] The layered double tetraamino-p-benzoquinone organic electrode material, conductive carbon black, and binder are mixed according to a mass ratio of 6:3:1 to prepare an electrode slurry, which is coated on a current collector and dried to make a positive electrode plate.

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

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

[0018] When the positive electrode sheet is used in a zinc-ion battery, metallic zinc is used as the negative electrode, and an aqueous zinc salt solution is used as the electrolyte.

[0019] The present invention focuses on the preparation of a layered bis(tetraamino-p-benzoquinone) (bTABQ) and its application as a positive electrode material for lithium-ion batteries. During the preparation of the material, the amount of the soft template agent added, as well as the heating temperature and stirring time, can be adjusted according to the actual situation.

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

[0021] 1. Highly ordered layered structure: By using a soft template agent for morphology-induced synthesis, a layered bTABQ material with a highly ordered structure was successfully prepared. This structure can maintain the structural stability of the electrode material during charge and discharge processes, significantly improving its cycle stability. In addition, the highly ordered layered structure also increases the specific surface area of the material, thereby expanding the effective contact area between the electrode material and the electrolyte, improving the utilization rate of active sites, and further enhancing the energy density of the electrode material.

[0022] 2. High crystallinity and exposure of active functional groups: The layered bTABQ material synthesized by morphology-induced synthesis exhibits excellent crystallinity. As Figure 9 shown, the sharpness of its (102) diffraction characteristic peak is significantly improved compared to the original bTABQ without morphology regulation, indicating a significant enhancement in the crystallinity of the material. This high crystallinity property contributes to the full exposure of active functional groups. As Figure 10 shown, under the same test conditions, the intensity of the infrared spectrum (ATR-IR) absorbance signal of the layered bTABQ is higher, indicating an increase in the exposure degree of active functional groups. This enhanced exposure degree of active sites is conducive to promoting the ion and electron transport efficiency, thus significantly improving the overall electrochemical performance of the material.

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

[0024] 4. Through reasonable molecular design and simple synthesis steps, the present invention successfully prepares an organic cathode material with a highly ordered layered structure, high crystallinity, high specific capacity, and good cycle stability. This material is expected to be applied in new high-performance batteries that are environmentally friendly and have high specific capacity.

[0025] 5. The layered bTABQ material provided by the present invention realizes the highly ordered crystal structure and the full exposure of functional group active sites through morphology control technology, significantly improving the cycle stability and reversible specific capacity (460 mAh·g -1 ), and the mass energy density is superior to that of traditional inorganic cathode materials. Brief Description of the Drawings

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

[0027] Figure 2 is Figure 1 partial enlarged view;

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

[0029] Figure 4 is Figure 3 partial enlarged view;

[0030] Figure 5 SEM image of the bulk bTABQ in Comparative Example 1;

[0031] Figure 6 is Figure 5 partial enlarged view;

[0032] Figure 7 SEM image of the layered bTABQ (large) in Comparative Example 2;

[0033] Figure 8 is Figure 7 partial enlarged view;

[0034] Figure 9 XRD comparison chart of the layered bTABQ in Example 1 and the original bTABQ;

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

[0036] Figure 11 Raman comparison chart of the layered bTABQ in Example 1 and the original bTABQ;

[0037] Figure 12 is for the layered bTABQ in Example 1 used in a lithium-ion battery at 0.1 A·g -1Charge-discharge cycle curve at a current density;

[0038] Figure 13 For the original bTABQ used in a lithium-ion battery at 0.1 A·g -1 Charge-discharge cycle curve at a current density;

[0039] Figure 14 For Comparative Example 1, bulk bTABQ used in a lithium-ion battery at 0.1 A·g -1 Charge-discharge cycle curve at a current density;

[0040] Figure 15 For Comparative Example 2, layered bTABQ (large) used in a lithium-ion battery at 0.1 A·g -1 Charge-discharge cycle curve at a current density;

[0041] Figure 16 For Example 1, layered bTABQ used in a sodium-ion battery at 0.1 A·g -1 Charge-discharge cycle curve at a current density;

[0042] Figure 17 For Example 1, layered bTABQ used in a zinc-ion battery at 0.1 A·g -1 Charge-discharge cycle curve at a current density. Detailed implementation manners

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

[0044] Example 1

[0045] A preparation method of a layered double-tetraamino-p-benzoquinone organic electrode material. Dissolve 0.6726 g of TABQ and 5.5584 g of TBACl (purity 85%) in 40 - 50 mL of DMF, stir and mix, and perform ultrasonic treatment to form a uniform mixed solution. Then transfer the mixed solution to a sealed reactor, place it in an environment of 125°C for reaction for 12 h. After the reaction ends, let the temperature of the reaction system drop to room temperature, wash and filter the product several times with DMF and methanol, and dry it to obtain the 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 by TBABr (purity 98%) to obtain layered bTABQ (large).

[0050] Figures 1 - 8 Scanning electron microscope (SEM) images of bTABQ in Example 1, Comparative Example 1, Comparative Example 2 during synthesis, and in the original state are shown respectively. From the image results, it can be seen that there are significant differences in the microstructural characteristics of different samples. Layered bTABQ presents a uniform small particle morphology 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 clustered structure; bulk bTABQ is also composed of uniform small particles but has no layered structure; while layered bTABQ (large) has larger and more evenly distributed particle sizes and also has a layered structure with an interlayer spacing between 0.04 - 0.05 μm.

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

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

[0053] Infrared spectroscopy (IR) characteristics: In the IR spectrum of layered bTABQ, the absorption peak intensities of key functional groups (such as C=O, N-H, etc.) are significantly enhanced and the peak widths become narrower. This characteristic indicates that the formation of the layered structure promotes the effective exposure of active functional groups.

[0054] Raman spectroscopy (Raman) characterization: The Raman peak intensity of layered bTABQ is higher and the full width at half maximum is smaller, reflecting an increase in the symmetry of the chemical bond vibration modes inside the material. Combining with the 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. In addition, the enhancement of the Raman peak intensity may imply a stronger electron-phonon coupling effect.

[0055] Application Example 1:

[0056] The bTABQ in Example 1, Comparative Example 1, Comparative Example 2, or its original state was mixed and ground with conductive carbon black (Super-p) and binder (polyvinylidene fluoride, PVDF) according to a mass ratio of 6:3:1. Subsequently, the obtained homogeneous mixture was mixed with an appropriate amount of N-methylpyrrolidone (NMP) to form a homogeneous electrode slurry. The electrode slurry was uniformly coated on an aluminum foil current collector by a doctor blade process, and the coating thickness was precisely controlled to 250 - 500 μm to ensure the uniformity and consistency of the electrode sheet. The coated aluminum foil current collector was placed in a vacuum oven at 105 - 110 °C for 12 hours of drying treatment to remove the solvent and cure 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] The assembly of coin cells was carried out in a glove box, where the oxygen and moisture concentrations in the environment were strictly controlled to not exceed 0.01 ppm. The assembly process was carried out in the following steps: First, the positive electrode case was placed on the operating table, and the positive electrode sheet prepared in Application Example 1 was placed as the positive electrode of the battery. Subsequently, a Celgard 2400 separator was stacked to separate the positive and negative electrodes and prevent short circuits, and an appropriate amount of electrolyte (1 M LiTFSI, with tetraethylene glycol dimethyl ether as the solvent) was dropped on the separator to provide an ion transport medium for the battery. Then, a lithium metal sheet was placed on the separator, and a spacer and a spring washer were stacked in sequence. Finally, the negative electrode case was covered on the top layer, and the battery was sealed using a battery encapsulation machine. The assembled battery was left to stand to allow the components inside to fully stabilize before performing electrochemical performance tests.

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

[0060] When assembling coin cells in a glove box, it was necessary to ensure that the oxygen and water vapor concentrations in the operating environment were lower than 0.01 ppm. The assembly process was carried out in the following steps: First, the negative electrode case was placed on the operating table, and a spring washer and a spacer were sequentially placed inside it. Subsequently, a sodium metal sheet negative electrode was placed on the spacer. Then, a glass fiber separator was stacked directly above the sodium sheet to ensure complete coverage of the negative electrode sheet, and then an electrolyte (1 M NaPF6, with diethylene glycol dimethyl ether as the solvent) was dropped on the separator. Next, the positive electrode sheet prepared in Application Example 1 was placed on the glass fiber separator. Finally, the positive electrode case was covered on the top layer, and the battery was sealed using a battery encapsulation machine. The assembled battery was left to stand to ensure the stability of the components inside the battery before performing electrochemical performance tests.

[0061] Application Example 4: Assembly of Zinc-Ion Batteries

[0062] The assembly of the aqueous zinc-ion button battery 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 case on the operating table, and then use tweezers to place the zinc foil negative electrode sheet in the negative electrode case. Next, lay a layer of glass fiber separator directly above the negative electrode sheet, and drop an appropriate amount of electrolyte (2M ZnSO4 aqueous solution) on the separator to ensure that it is fully wetted. Then, place the positive electrode sheet prepared in Application Example 1 flat above the glass fiber separator, and stack a spacer and a spring sheet on it in sequence. Finally, cover the positive electrode case on the top layer and use a battery encapsulation machine for sealing. After the assembly is completed, let the battery stand for a period of time to ensure the stability of each component inside the battery, and then the electrochemical performance test can be carried out.

[0063] Figures 12 - 15 The charge-discharge curves of the batteries with layered bTABQ, pristine bTABQ, bulk bTABQ, and layered bTABQ (large) as the positive electrode materials for lithium-ion batteries are presented. At the same time, Figure 16 and Figure 17 show the charge-discharge curves of layered bTABQ when used as the positive electrode material for sodium-ion batteries and aqueous zinc-ion batteries respectively at a current density of 0.1 A·g -1 current density.

[0064] In the electrochemical performance test of lithium-ion batteries, layered bTABQ exhibits excellent performance. At a current density of 0.1 A·g -1 , its discharge specific capacity is as high as 460 mAh·g -1 , with a clear discharge plateau and excellent cycle stability. In contrast, the discharge specific capacity of pristine bTABQ at the same current density is about 325 mAh·g -1 , and the voltage plateau is relatively flat. The specific capacity of bulk bTABQ is significantly lower, about 250 mAh·g -1 , not only with an unclear voltage plateau but also with a prominent specific capacity decay phenomenon. Layered bTABQ (large) also has the problem of an unclear voltage plateau and poor cycle 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 are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the inventive concept, several deformations and improvements can still be made, and these all belong to the protection scope of the present invention.

Claims

1. A layered double tetraamino-p-benzoquinone organic electrode material, characterized in that The chemical formula of the said material is C 12 H8N6O4, which has a highly ordered layered structure with an interlayer spacing of 0.02 - 0.03 μm, and its molecular structure is as follows: 。 2. A preparation method of the layered double tetraamino-p-benzoquinone organic electrode material as described in claim 1, characterized in that, Dissolve tetraaminobenzoquinone and a soft template agent in an organic solvent to form a homogeneous mixed solution. Heat the solution to 100 - 150 °C and react for 12 - 24 hours. Then cool down the temperature, wash the solid, and perform suction filtration to obtain a layered double tetraaminobenzoquinone material. The soft template agent is one or more of tetrabutylammonium chloride, tetraethylammonium chloride, and tetramethylammonium chloride.

3. The preparation method of the layered double tetraamino-p-benzoquinone organic electrode material according to claim 2, characterized in that, The mass ratio of the tetraaminobenzoquinone to the soft template agent is 0.6 - 0.7:5.0 - 6.

0.

4. The preparation method of the layered double tetraamino-p-benzoquinone organic electrode material according to claim 2, characterized in that, The organic solvent is one or more of N, N - dimethylformamide, N - methylpyrrolidone, N, N - dimethylacetamide, and methanol.

5. The preparation method of the layered double tetraamino-p-benzoquinone organic electrode material according to claim 2, wherein The soft template agent is tetrabutylammonium chloride, and the purity of tetrabutylammonium chloride is 85%.

6. Application of the layered double tetraaminobenzoquinone organic electrode material as described in claim 1 in lithium - ion batteries, sodium - ion batteries, and zinc - ion batteries.

7. The application according to claim 6, characterized in that, Mix the layered double tetraaminobenzoquinone organic electrode material, conductive carbon black, and binder according to a mass ratio of 6:3:1 to prepare an electrode slurry, and coat it on a current collector and dry it to make a positive electrode plate.

8. The application according to claim 7, wherein When the positive electrode plate is used in a lithium - ion battery, the negative electrode uses metallic lithium, and the electrolyte uses a lithium salt ether solution.

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

10. The application according to claim 7, characterized in that, When the positive electrode plate is used in a zinc - ion battery, the negative electrode uses metallic zinc, and the electrolyte uses an aqueous zinc salt solution.

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