Organic supramolecular conjugated polymer, preparation method thereof and potassium ion battery

Abstract

The invention discloses an organic supramolecular conjugated polymer, a preparation method thereof and a potassium ion battery, and belongs to the technical field of batteries. Tetraaminobenzoquinone and sodium chloride are uniformly mixed to obtain a mixture A, and then the mixture A and a hydrochloric acid solution are subjected to ball milling to obtain red brown powder; reacting the red brown powder with a sulfuric acid solution, filtering precipitates, and performing vacuum drying to obtain dark green powder; placing the dark green powder in absolute ethyl alcohol to react, filtering, and drying the filtered substance in vacuum to obtain the organic supramolecular conjugated polymer. The organic supramolecular conjugated polymer disclosed by the invention has active sites with higher density and prolonged pi conjugated molecular chains, ensures high theoretical capacity, can enhance intrinsic conductivity to realize efficient utilization of the active sites, has more excellent cycle stability, and solves the problem that the organic polymer has a large specific surface area in a potassium ion battery. And high capacity, high conductivity and excellent stability are difficult to synergistically improve.

Description

Technical Field

[0001] The present invention relates to the technical field of batteries, and particularly to an organic supramolecular conjugated polymer, a preparation method thereof, and a potassium ion battery. Background Art

[0002] Currently, the global goal of addressing climate change and promoting sustainable energy development has given rise to a huge demand for renewable energy, thereby posing unprecedented challenges to large-scale, efficient, and economic energy storage technologies. The rapid development in areas such as the development and utilization of marine resources, grid stability, off-grid power supply, electric transportation, and portable devices all urgently require energy storage solutions with excellent performance, controllable costs, and sustainable resources. Although lithium-ion batteries currently dominate, the limited resources and rising prices of their core raw material lithium, as well as their impact on the environment, are increasingly becoming bottlenecks restricting their further widespread application. It is precisely against the grand background of the global energy transition and the search for sustainable energy storage alternatives that potassium ion batteries have emerged as a strong competitor. Their core advantages lie in their extremely abundant resources, low cost, and similar working principles to lithium-ion batteries, which endow them with important strategic significance and broad application potential in building a future-oriented and sustainable global energy system.

[0003] In the exploration of next-generation potassium ion batteries, organic electrode materials have attracted much attention due to their unique advantages. Compared with inorganic materials, the highly designable molecular structure is crucial, enabling precise regulation of electrochemical properties to match large-sized potassium ions and theoretically achieving high capacity and appropriate voltage platforms. Organic materials have a lower density, which is beneficial for volumetric energy density; many precursors are widely available and inexpensive, meeting the low-cost goal. They are flexible, environmentally friendly, and easy to recycle, providing possibilities for flexible batteries and sustainable development. Based on rapid molecular redox, high rate performance can theoretically be achieved. However, organic electrode materials face significant disadvantages in the application of potassium ion batteries: most have poor conductivity and require a large amount of conductive agents; they are easily dissolved or swollen in the electrolyte, resulting in loss of activity and damage to cycle stability; the surface is prone to side reactions with the electrolyte to form an unstable solid electrolyte interface; the diffusion of large-sized potassium ions is slow, and the molecular structure is easily irreversibly degraded, limiting high rate and long-term stability. Overcoming core challenges such as conductivity and solubility is the key to promoting the practical application of organic potassium ion batteries.

[0004] To improve the stability and cycling performance of organic electrode materials in potassium-ion batteries, polymerization strategies have been widely adopted to reduce the solubility of small molecules in electrolytes and enhance structural integrity. Although polymerization has improved the lifespan of electrode materials to some extent, many challenges still remain. On the one hand, non-active groups are often introduced during the polymerization process, diluting the effective electrochemical reaction sites and resulting in a decrease in the theoretical capacity of organic electrode materials. On the other hand, polymers have poor conductivity themselves, and conductive agents usually need to be introduced or composite structures need to be constructed to improve the overall performance, increasing the synthesis complexity and cost. In addition, the packing of polymer chains may hinder the diffusion of potassium ions inside the material, affecting its rate performance. The polymerization reaction path is often complex, with poor control over molecular weight distribution and structure, which also limits the consistency of material performance and the feasibility of large-scale preparation. Therefore, how to optimize capacity, conductivity, and ion transport performance while improving stability remains a key issue for the polymerization strategy in the preparation of organic electrode materials. Summary of the Invention

[0005] The object of the present invention is to overcome the challenges such as the reduction of the theoretical capacity and insufficient conductivity of the battery after the use of organic electrode materials due to the deficiencies of existing processes during the application of organic electrode materials. The present invention proposes an organic supramolecular conjugated polymer, its preparation method, and a potassium-ion battery. This method uses commercially available tetraaminobenzoquinone (TABQ) as a synthesis monomer, combines a unique ball-milling process to synthesize a polymer precursor, and then obtains an organic supramolecular conjugated polymer, namely poly-tetraaminobenzoquinone organic electrode material (pTABQ), through a subsequent solution polymerization strategy. This organic supramolecular conjugated polymer, through a self-polymerization strategy, not only does not introduce non-active groups but also removes some non-active groups, further increasing the density of redox active sites. Secondly, the extended conjugated structure expands the degree of electron delocalization, effectively enhancing the conductivity of the organic electrode material. Finally, the complex intermolecular forces within the organic supramolecular conjugated polymer endow it with excellent cycle stability. It solves the problem that it is difficult to synergistically improve high capacity, high conductivity, and excellent stability in organic polymers for potassium-ion batteries. This modification method of organic polymers has many advantages such as obvious improvement effect, simple synthesis process, and low production cost, can achieve the large-scale production of organic supramolecular conjugated polymers, and effectively promote the practical application of potassium-ion batteries; its application in new and efficient energy storage devices, such as developing high-performance marine energy storage batteries, grid energy storage batteries, and electric transportation energy storage batteries, has significant scientific value and practical application prospects.

[0006] The technical solution of the present invention is realized as follows: A preparation method of an organic supramolecular conjugated polymer, comprising the following steps: S1. Add tetraaminobenzoquinone and sodium chloride into a mortar and grind them evenly to obtain mixture A; the mass ratio of tetraaminobenzoquinone to sodium chloride is 1-2:20; S2. Transfer mixture A to a ball milling jar, add hydrochloric acid solution and then conduct ball milling treatment to obtain mixture B; S3. Transfer mixture B to sulfuric acid solution, heat and boil it, then filter, collect the precipitate, wash it with deionized water and conduct vacuum high-temperature drying to obtain a powder; The specific steps of step S4 are as follows: transfer the obtained powder to absolute ethanol, and stir it for 48-72 hours under the condition that the stirring speed is 300-400 revolutions per minute, filter and conduct vacuum drying at 60-70 °C for 6-7 hours to obtain an organic supramolecular conjugated polymer.

[0007] Further, in step S1, the grinding time is 10-20 minutes.

[0008] Further, in step S2, agate ball milling beads and a nylon ball milling jar are used in the ball milling treatment process, and then the nylon ball milling jar is fixed in a planetary ball mill for ball milling treatment; the mass ratio of the agate ball milling beads to mixture A is 30-50:1; the particle sizes of the agate ball milling beads are 3 mm, 6 mm, and 8 mm respectively, and the quantity ratio is 4-2:3-2:1.

[0009] Further, in step S2, the rotation speed of the ball milling treatment is 320-380 revolutions per minute, and the ball milling time is 10-15 minutes.

[0010] Further, in step S2, the concentration of the hydrochloric acid solution is 10-12 mol / L; in step S3, the concentration of the sulfuric acid solution is 0.02-0.03 mol / L.

[0011] Further, the mass-volume ratio of tetraaminobenzoquinone, hydrochloric acid solution, and sulfuric acid solution is 1-4 g:1-4 mL:400-600 mL.

[0012] Further, in step S3, the vacuum high-temperature drying temperature is 60-70 °C and the drying time is 5-7 hours.

[0013] Further, in step S4, the material-liquid ratio of the powder to absolute ethanol in mg / mL is 1~3:1.

[0014] The organic supramolecular conjugated polymer prepared by the preparation method of the present invention.

[0015] Further, the organic supramolecular conjugated polymer is applied in the preparation of potassium ion batteries.

[0016] Compared with the prior art, the beneficial effects of the present invention are: 1. The present invention uses commercially available tetraaminobenzoquinone (TABQ) as a synthesis monomer, and obtains an organic supramolecular conjugated polymer through a self-polymerization strategy, namely a poly(tetraaminobenzoquinone) organic electrode material (pTABQ). By increasing the density of matrix redox active sites, extending the π-conjugated molecular chain, and endowing the polymer with more complex intermolecular forces, the challenge of difficult to synergistically improve the high capacity, high intrinsic conductivity, and high cycle stability during the process of improving the energy storage potential of organic electrode materials by using the polymerization strategy is solved.

[0017] 2. The preparation method of the present invention does not require high-temperature firing. Hydrochloric acid, sulfuric acid, anhydrous ethanol and other raw materials are used to prepare the poly(tetraaminobenzoquinone) organic electrode material, which has outstanding advantages such as low-cost raw materials, green process, high yield, and easy large-scale production. At the same time, it exhibits excellent electrochemical performance. The proposed method provides a general and efficient optimization path for the polymerization of organic small molecules, significantly improving the theoretical capacity, intrinsic conductivity, and cycle stability of the materials. Under the dual demands of high energy density and reliability in large-scale energy storage systems, this type of organic electrode material with both fast kinetic response and durability shows broad application prospects. Brief Description of the Drawings

[0018] Figure 1 is the X-ray diffraction pattern of the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) prepared in Example 1, where 2θ in the figure refers to the diffraction angle; Figure 2 is the infrared spectrum of the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) prepared in Example 1; Figure 3 is the Raman spectrum of the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) prepared in Example 1; Figure 4 is the molecular structure diagram of the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) prepared in Example 1; Figure 5 is the electron paramagnetic energy spectrum of the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) prepared in Example 1; Figure 6 is the thermogravimetric diagram of the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) prepared in Example 1; Figure 7 is the full-spectrum comparison diagram of the photoelectron spectra of the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) and tetraaminobenzoquinone (TABQ) prepared in Example 1; Figure 8 is the charge-discharge curve of the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) assembled into a button-type potassium ion battery at a current density of 100 mA / g. Detailed Embodiments

[0019] To better understand the technical content of the present invention, specific embodiments are provided below to further illustrate the present invention.

[0020] Unless otherwise specified, the experimental methods used in the embodiments of the present invention are all conventional methods.

[0021] Unless otherwise specified, the materials, reagents, etc. used in the embodiments of the present invention can all be obtained from commercial channels.

[0022] Example 1 A preparation method of an organic supramolecular conjugated polymer, comprising the following steps: S1. Add 1 g of tetraaminobenzoquinone and 20 g of sodium chloride to an agate mortar, and grind thoroughly until a black mixture A without obvious white powder is obtained; S2. Add the black mixture A obtained in step S1 into a nylon ball mill jar equipped with agate ball milling beads. The mass ratio of the agate ball milling beads to the mixture A is 40:1; the particle sizes of the agate ball milling beads are 3 mm, 6 mm, and 8 mm respectively, and the quantity ratio is 4:3:1; then add 2 ml of a concentrated hydrochloric acid solution with a concentration of 12 mol / L, and then place the nylon ball mill jar in a planetary ball mill and perform ball milling treatment at a ball milling speed of 320 revolutions per minute for 12 minutes to obtain a reddish-brown mixture B; S3. Transfer the reddish-brown mixture B obtained in step S2 to a 1 L round-bottom flask, add 500 ml of a dilute sulfuric acid solution with a concentration of 0.02 mol / L to the round-bottom flask and heat to boiling, collect the precipitate by filtration, wash the precipitate 3 times with deionized water, and then place it in a vacuum environment and dry it in an oven at a set temperature of 70 °C for 7 h to obtain a dark green powder; S4. Take 200 mg of the dark green powder obtained in step S3, put it into 100 ml of absolute ethanol, and perform solution polymerization treatment by stirring at a stirring speed of 300 revolutions per minute for 72 hours, filter, and then place the filtrate in a vacuum environment and dry it in an oven at a set temperature of 70 °C for 7 h to obtain an organic supramolecular conjugated polymer, which is a poly(tetraaminobenzoquinone) organic electrode material, denoted as pTABQ.

[0023] Figure 1 This is the X-ray diffraction pattern of the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) synthesized in the present invention. As Figure 1 shown, the strong π peak near 28.3° corresponds to the π stacking feature, indicating that there is a strong intermolecular π interaction in the direction of this crystal plane.

[0024] As Figure 2 shown in the infrared spectrum, in addition to the characteristic oscillation peaks derived from carbonyl, amino, and benzene rings, at 3450 cm -1There are also multiple oscillation peaks near the origin, which are generated by the interaction between amino, amine hydrogen and carbonyl oxygen, indicating that there are abundant hydrogen bond interactions between the molecular chains of the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) synthesized in the present invention.

[0025] As Figure 3 shown in the Raman spectrum, the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) synthesized in the present invention shows a broad characteristic peak at 2800 cm -1 , which is a typical characteristic of the hydrogen bond network. The ID / IG ratio is 0.81, indicating that the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) has a graphite-like layer structure.

[0026] As Figure 4 shown in the molecular structure diagram, the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) synthesized in the present invention forms a molecular chain in one-dimensional direction by removing amino linkages. This long-chain structure has a high degree of electron delocalization and plays an important role in conductivity.

[0027] As Figure 5 shown in the electron energy spectrum, the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) synthesized in the present invention has an obvious Gaussian signal, indicating that pTABQ has potential high conductivity characteristics.

[0028] As Figure 6 shown in the thermogravimetric diagram, the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) synthesized in the present invention benefits from its abundant intermolecular forces and begins to decompose significantly near 400 °C, showing very excellent thermal stability.

[0029] As Figure 7 shown, compared with commercial tetraaminobenzoquinone (TABQ), the nitrogen content of the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) synthesized in the present invention is significantly reduced. This is because during the synthesis of pTABQ, TABQ forms chains by removing amino groups, so the nitrogen content is low.

[0030] Example 2 An organic supermolecular conjugated polymer (pTABQ) obtained in Example 1 above was used to assemble a button-type potassium ion battery, as follows: Using the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) prepared in Example 1 of the present invention as the negative electrode active material of the potassium ion battery, conductive carbon black as the conductive agent, and carboxymethyl cellulose as the binder; the mass ratio of the active material, conductive agent, and binder is 6:3:1. After mixing them in proportion, deionized water was added to make a slurry, which was evenly coated on the copper foil. The electrode sheet was made by stamping the copper foil into a circular sheet with a diameter of 10 mm, and the mass loading of the stamped electrode sheet was 0.8 - 1.2 mg / cm -2, The CR2016 button battery was assembled in an argon glove box. Potassium metal sheet and glass fiber filter paper (GF / F) were used as the counter electrode and separator respectively. The potassium ion electrolyte was 5M KFSI dissolved in ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (the volume ratio of the solvents was 1:1).

[0031] In this example, the charge-discharge curve of the button-type potassium ion battery assembled with the organic supramolecular conjugated polymer and the potassium metal electrode sheet at a small current density of 100 mA / g is as Figure 8 shown: The poly(tetraaminobenzoquinone) organic electrode material (pTABQ) exhibits a pair of significant redox peaks and shows high electrochemical activity, with a capacity exceeding 400 mAh / g.

[0032] In the button-type potassium ion battery assembled with the organic supramolecular conjugated polymer and the potassium metal electrode sheet, under long cycling at a large current density of 2000 mA / g, the poly(tetraaminobenzoquinone) organic electrode material (pTABQ) benefits from its multiple redox active sites and a high degree of electron delocalization. pTABQ has the characteristics of high capacity and high conductivity. Therefore, it still exhibits a high capacity of more than 220 mAh / g at a large current of 2000 mA / g. In addition, the abundant intermolecular forces endow pTABQ with excellent cycle stability. After cycling more than 500 times, the capacity retention rate is close to 100%.

[0033] Example 3 A preparation method of an organic supramolecular conjugated polymer is as follows: S1. Add 2 grams of tetraaminobenzoquinone and 20 grams of sodium chloride into an agate mortar, and grind thoroughly until a black mixture A without obvious white powder is obtained; S2. Add the black mixture A obtained in step S1 into a nylon ball milling tank equipped with agate ball milling beads. The mass ratio of the agate ball milling beads to the mixture A is 50:1; the particle sizes of the agate ball milling beads are 3 mm, 6 mm, and 8 mm respectively, and the quantity ratio is 4:2:1; then add 2 ml of concentrated hydrochloric acid solution with a concentration of 12 mol / L, and then place the ball milling tank in a planetary ball mill and carry out ball milling treatment at a ball milling speed of 350 revolutions per minute for 12 minutes to obtain a reddish-brown mixture B; S3. Transfer the reddish-brown mixture B obtained in step S2 to a 1 L round-bottom flask, add 500 ml of dilute sulfuric acid solution with a concentration of 0.03 mol / L to the round-bottom flask and heat to boiling. Collect the precipitate by filtration, wash the precipitate 3 times with deionized water and ethanol, and then place it in an oven under vacuum at a set temperature of 60 °C and dry for 5 h to obtain a dark green powder; S4. Take 200 mg of the dark green powder obtained in step S3, put it into 100 ml of absolute ethanol, and stir for 60 hours at a stirring speed of 350 revolutions per minute for solution polymerization treatment. Then filter, and put the filtrate into an oven at a set temperature of 70 °C in a vacuum environment and dry for 6 h to obtain an organic supramolecular conjugated polymer, which is the poly(tetraaminobenzoquinone) organic electrode material, denoted as pTABQ.

[0034] Example 4 A preparation method of an organic supramolecular conjugated polymer, the specific steps are as follows: S1. Add 1 g of tetraaminobenzoquinone and 20 g of sodium chloride into an agate mortar, and grind thoroughly until a black mixture A without obvious white powder is obtained; S2. Add the black mixture A obtained in step S1 into a nylon ball mill jar equipped with agate ball mill beads. The mass ratio of the agate ball mill beads to the mixture A is 30:1; the particle sizes of the agate ball mill beads are 3 mm, 6 mm, and 8 mm respectively, and the quantity ratio is 2:3:1; then add 2 ml of concentrated hydrochloric acid solution with a concentration of 12 mol / L, and then place the nylon ball mill jar in a planetary ball mill and carry out ball milling treatment at a ball milling speed of 360 revolutions per minute for 15 minutes to obtain a reddish-brown mixture B; S3. Transfer the reddish-brown mixture B obtained in step S2 to a 1 L round-bottom flask, add 500 ml of dilute sulfuric acid solution with a concentration of 0.03 mol / L to the round-bottom flask and heat to boiling. Collect the precipitate by filtration, wash the precipitate 3 times with deionized water and ethanol, and then put it into an oven at a set temperature of 70 °C in a vacuum environment and dry for 5 h to obtain a dark green powder; S4. Take 200 mg of the dark green powder obtained in step S3, put it into 100 ml of absolute ethanol, and stir for 48 hours at a stirring speed of 400 revolutions per minute for solution polymerization treatment. Then filter, and put the filtrate into an oven at a set temperature of 60 °C in a vacuum environment and dry for 7 h to obtain the poly(tetraaminobenzoquinone) organic electrode material, which is the organic supramolecular conjugated polymer, denoted as pTABQ.

[0035] Example 5 A preparation method of an organic supramolecular conjugated polymer, including the following steps: S1. Add 1 g of tetraaminobenzoquinone and 20 g of sodium chloride into an agate mortar, and grind thoroughly until a black mixture without obvious white powder is obtained; S2. Add the black mixture obtained in step S1 into a nylon ball mill jar filled with agate ball mill beads. The mass ratio of the agate ball mill beads to mixture A is 40:1. The particle sizes of the agate ball mill beads are 3 mm, 6 mm, and 8 mm respectively, and the quantity ratio is 3:2:1. Then add 2 ml of concentrated hydrochloric acid solution with a concentration of 12 mol / L, and place the nylon ball mill jar in a planetary ball mill for ball milling treatment at a ball milling speed of 380 revolutions per minute for 10 minutes to obtain a reddish-brown mixture B. S3. Transfer the reddish-brown mixture B obtained in step S2 to a 1-L round-bottom flask, add 500 ml of dilute sulfuric acid solution with a concentration of 0.02 mol / L to the round-bottom flask and heat it to boiling. Collect the precipitate by filtration, wash the precipitate 3 times with deionized water and ethanol, and then place it in an oven under a vacuum environment at a set temperature of 70 °C for drying for 6 h to obtain a dark green powder. S4. Take 200 mg of the dark green powder obtained in step S3, put it into 100 ml of absolute ethanol, and carry out solution polymerization treatment by stirring at a stirring speed of 400 revolutions per minute for 48 hours. Filter, and then place the filtrate in an oven under a vacuum environment at a set temperature of 60 °C for drying for 7 h to obtain an organic supramolecular conjugated polymer, which is the poly(tetraaminobenzoquinone) organic electrode material, denoted as pTABQ.

[0036] Comparative Example 1 In this invention, on the basis of Example 1, the absolute ethanol in step S4 is replaced with acetonitrile, and the rest is the same as in Example 1.

[0037] A preparation method of an organic supramolecular conjugated polymer in this comparative example includes the following steps: S1. Add 1 g of tetraaminobenzoquinone and 20 g of sodium chloride into an agate mortar, and grind thoroughly until a black mixture A without obvious white powder is obtained. S2. Add the black mixture A obtained in step S1 into a nylon ball mill jar filled with agate ball mill beads. The mass ratio of the agate ball mill beads to mixture A is 40:1. The particle sizes of the agate ball mill beads are 3 mm, 6 mm, and 8 mm respectively, and the quantity ratio is 4:3:1. Then add 2 ml of concentrated hydrochloric acid solution with a concentration of 12 mol / L, and place the nylon ball mill jar in a planetary ball mill for ball milling treatment at a ball milling speed of 320 revolutions per minute for 12 minutes to obtain a reddish-brown mixture B. S3. Transfer the reddish-brown mixture B obtained in step S2 to a 1-L round-bottom flask, add 500 ml of dilute sulfuric acid solution with a concentration of 0.02 mol / L to the round-bottom flask and heat it to boiling. Collect the precipitate by filtration, wash the precipitate 3 times with deionized water, and then place it in an oven under a vacuum environment at a set temperature of 70 °C for drying for 7 h to obtain a dark green powder. S4. Take 200 mg of the dark green powder obtained in step S3 and put it into 100 ml of acetonitrile. Stir for 72 hours at a stirring speed of 300 revolutions per minute for solution polymerization treatment. Then filter, and put the filtrate into an oven under vacuum at a set temperature of 70 °C for drying for 7 hours to obtain an organic supramolecular conjugated polymer, which is the poly(tetraaminobenzoquinone) organic electrode material, denoted as pTABQ.

[0038] The button-type potassium-ion battery assembled with the organic supramolecular conjugated polymer prepared in this comparative example and a potassium metal electrode sheet was subjected to long cycling at a high current density of 2000 mA / g. It was found that its capacity was 180 mAh / g, and after more than 500 cycles, the capacity retention rate was 94%. The performance effect was lower than that of the poly(tetraaminobenzoquinone) organic electrode material prepared in Example 1.

[0039] Comparative Example 2 In the present invention, on the basis of Example 1, the absolute ethanol in step S4 was replaced with an ethanol solution with a volume concentration of 70%, and the rest was the same as in Example 1.

[0040] A preparation method of an organic supramolecular conjugated polymer in this comparative example includes the following steps: S1. Add 1 g of tetraaminobenzoquinone and 20 g of sodium chloride to an agate mortar and grind thoroughly until a black mixture A without obvious white powder is obtained. S2. Add the black mixture A obtained in step S1 into a nylon ball mill jar equipped with agate ball mill beads. The mass ratio of the agate ball mill beads to the mixture A is 40:1; the particle sizes of the agate ball mill beads are 3 mm, 6 mm, and 8 mm respectively, and the quantity ratio is 4:3:1; then add 2 ml of a concentrated hydrochloric acid solution with a concentration of 12 mol / L, and then place the nylon ball mill jar in a planetary ball mill for ball milling at a ball milling speed of 320 revolutions per minute for 12 minutes to obtain a reddish-brown mixture B. S3. Transfer the reddish-brown mixture B obtained in step S2 to a 1 L round-bottom flask, add 500 ml of a dilute sulfuric acid solution with a concentration of 0.02 mol / L to the round-bottom flask and heat to boiling. Collect the precipitate by filtration, wash the precipitate 3 times with deionized water, and then put it into an oven under vacuum at a set temperature of 70 °C for drying for 7 hours to obtain a dark green powder. S4. Take 200 mg of the dark green powder obtained in step S3 and put it into 100 ml of an ethanol solution with a volume concentration of 70%. Stir for 72 hours at a stirring speed of 300 revolutions per minute for solution polymerization treatment. Then filter, and put the filtrate into an oven under vacuum at a set temperature of 70 °C for drying for 7 hours to obtain an organic supramolecular conjugated polymer, which is the poly(tetraaminobenzoquinone) organic electrode material, denoted as pTABQ.

[0041] The button-type potassium-ion battery assembled with the organic supramolecular conjugate polymer prepared in this comparative example and a potassium metal electrode sheet was subjected to long cycling at a high current density of 2000 mA / g. It was found that its capacity was 190 mAh / g, and after more than 500 cycles, the capacity retention rate was 95%. The performance was lower than that of the poly(tetraaminobenzoquinone) organic electrode material prepared in Example 1.

[0042] The results of Comparative Example 1 and Comparative Example 2 above show that by using hydrochloric acid, sulfuric acid, absolute ethanol, etc. as raw materials to prepare the poly(tetraaminobenzoquinone) organic electrode material, the present invention can endow it with good performance.

[0043] The above are only the preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims

1. A preparation method of an organic supramolecular conjugated polymer, characterized in that, It includes the following steps: S1. Add tetraaminobenzoquinone and sodium chloride into a mortar and grind them evenly to obtain mixture A; the mass ratio of tetraaminobenzoquinone to sodium chloride is 1-2:20; S2. Transfer mixture A to a ball milling tank, add hydrochloric acid solution and then carry out ball milling treatment to obtain mixture B; S3. Transfer mixture B to sulfuric acid solution, heat and boil it, then filter, collect the precipitate, wash it with deionized water and carry out vacuum high-temperature drying to obtain a powder; S4. Transfer the obtained powder to absolute ethanol, stir it at a stirring speed of 300-400 revolutions per minute for 48-72 hours, filter and carry out vacuum drying at 60-70 °C for 6-7 hours to obtain an organic supramolecular conjugated polymer.

2. The preparation method of the organic supramolecular conjugated polymer according to claim 1, characterized in that, In step S2, agate ball milling beads and a nylon ball milling tank are used in the ball milling process, and then the nylon ball milling tank is fixed in a planetary ball mill for ball milling treatment; the mass ratio of the agate ball milling beads to mixture A is 30-50:1; the particle sizes of the agate ball milling beads are 3 mm, 6 mm, and 8 mm respectively, and the quantity ratio is 4-2:3-2:

1.

3. The preparation method of the organic supramolecular conjugated polymer according to claim 1, characterized in that, In step S2, the rotation speed of the ball milling treatment is 320-380 revolutions per minute, and the ball milling time is 10-15 minutes.

4. The preparation method of the organic supramolecular conjugated polymer according to claim 1, wherein In step S2, the concentration of the hydrochloric acid solution is 12 mol / L; in step S3, the concentration of the sulfuric acid solution is 0.02-0.03 mol / L.

5. The preparation method of the organic supramolecular conjugated polymer according to claim 1, characterized in that, The mass-volume ratio of the tetraaminobenzoquinone, hydrochloric acid solution, and sulfuric acid solution is 1-4 g:1-4 mL:400-600 mL.

6. The preparation method of the organic supramolecular conjugated polymer according to claim 1, characterized in that, In step S3, the vacuum high-temperature drying temperature is 60-70 °C, and the drying time is 5-7 hours.

7. The preparation method of the organic supramolecular conjugated polymer according to claim 1, wherein In step S4, the material-liquid ratio of the powder to absolute ethanol (mg / mL) is 1~3:

1.

8. An organic supramolecular conjugated polymer prepared by the preparation method according to any one of claims 1-7.

9. The organic supramolecular conjugated polymer according to claim 8, wherein, The application of the organic supramolecular conjugated polymer in the preparation of potassium ion batteries.

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