An organic supramolecular conjugated polymer and its preparation method and potassium ion battery

Abstract

The present invention discloses an organic supramolecular conjugated polymer, a preparation method thereof, and a potassium ion battery, belonging to the field of battery technology. The present invention mixes tetraaminobenzoquinone and sodium chloride to obtain a mixture A, and then ball-mills the mixture with a hydrochloric acid solution to obtain a reddish-brown powder; the reddish-brown powder is reacted with a sulfuric acid solution, and the precipitate is filtered and vacuum-dried to obtain a dark green powder; the dark green powder is placed in anhydrous ethanol for reaction, filtered, and the filtrate is vacuum-dried to obtain an organic supramolecular conjugated polymer. The organic supramolecular conjugated polymer of the present invention has a higher density of active sites and an extended π-conjugated molecular chain, which can enhance the intrinsic conductivity while ensuring a high theoretical capacity to achieve efficient utilization of active sites, and has better cycle stability, solving the problem that the high capacity, high conductivity, and excellent stability of organic polymers in potassium ion batteries are difficult to synergistically improve.

Description

Technical Field

[0001] The present invention relates to the technical field of batteries, and in particular 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 driven a massive demand for renewable energy, posing unprecedented challenges for large-scale, efficient, and cost-effective energy storage technologies. The rapid development of marine resource development and utilization, grid stability, off-grid power supply, electric transportation, and portable devices all urgently requires high-performance, cost-effective, and sustainable energy storage solutions. Although lithium-ion batteries currently dominate, the limited availability and rising price of their core raw material, lithium, as well as their environmental impact, are increasingly hindering their widespread adoption. Against the backdrop of global energy transition and the search for sustainable energy storage alternatives, potassium-ion batteries have emerged as a strong contender. Their core advantages lie in their abundant resources, low cost, and similar operating principles to lithium-ion batteries. These characteristics give them significant strategic significance and broad application potential in building a future-oriented, sustainable energy system worldwide.

[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 key, allowing for precise control of electrochemical properties to adapt to large-sized potassium ions, theoretically achieving high capacity and a suitable voltage platform. Organic materials have a low density, which is beneficial for volumetric energy density; many precursors are widely available and low-cost, meeting the low-cost goal. They are flexible, environmentally friendly, and easily recyclable, providing possibilities for flexible batteries and sustainable development. Based on rapid molecular redox, they can theoretically achieve high rate performance. However, organic electrode materials face significant disadvantages in potassium-ion battery applications: most have poor conductivity and require large amounts of conductive agents; they easily dissolve or swell in the electrolyte, resulting in loss of activity and impaired cycling stability; their surfaces are prone to side reactions with the electrolyte to form unstable solid-electrolyte interfaces; large-sized potassium ions diffuse slowly, and their molecular structure is prone to irreversible degradation, limiting high rate and long-term stability. Overcoming core challenges such as conductivity and solubility is key to promoting the practical application of organic potassium-ion batteries.

[0004] In order to improve the stability and cycle performance of organic electrode materials in potassium ion batteries, polymerization strategies have been widely adopted to reduce the solubility of small molecules in the electrolyte and enhance structural integrity. Although polymerization has improved the life of electrode materials to a certain extent, it still faces many challenges. On the one hand, inactive groups are often introduced during the polymerization process, which dilutes the effective electrochemical reaction sites and leads to a decrease in the theoretical capacity of organic electrode materials. On the other hand, the polymer itself has poor conductivity, and it is usually necessary to introduce conductive agents or construct composite structures to improve the overall performance, which increases the complexity and cost of the synthesis. In addition, the stacking of polymer chains may hinder the diffusion of potassium ions within the material, affecting its rate performance. The polymerization reaction path is often complex, and the molecular weight distribution and structural controllability are poor, 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 facing the polymerization strategy for preparing organic electrode materials. Summary of the Invention

[0005] The present invention aims to overcome challenges in the application of organic electrode materials, such as reduced theoretical capacity and insufficient conductivity after use due to deficiencies in existing processes. The present invention proposes an organic supramolecular conjugated polymer, a preparation method, and a potassium-ion battery. This method uses commercial tetraaminobenzoquinone (TABQ) as a synthetic monomer, combined with a unique ball milling process to synthesize a polymer precursor. A subsequent solution polymerization strategy yields an organic supramolecular conjugated polymer, namely polytetraaminobenzoquinone (pTABQ), an organic electrode material. This organic supramolecular conjugated polymer utilizes a self-polymerization strategy to remove some inactive groups without introducing them, further increasing the density of redox-active sites. Furthermore, the extended conjugated structure maximizes electron delocalization, effectively enhancing the conductivity of the organic electrode material. Finally, the complex intermolecular forces within the organic supramolecular conjugated polymer impart excellent cycling stability. This overcomes the challenge of achieving high capacity, high conductivity, and excellent stability in potassium-ion batteries using organic polymers. This organic polymer modification method has many advantages, such as obvious improvement effect, simple synthesis process and low production cost. It can realize the large-scale production of organic supramolecular conjugated polymers and effectively promote the practical application of potassium ion batteries. The application of this organic supramolecular conjugated polymer in new high-efficiency energy storage devices and the development of high-performance marine energy storage batteries, grid energy storage batteries, electric transportation energy storage batteries, etc. have significant scientific value and practical application prospects.

[0006] The technical solution of the present invention is achieved as follows:

[0007] A method for preparing an organic supramolecular conjugated polymer comprises the following steps:

[0008] S1. Add tetraaminobenzoquinone and sodium chloride into a mortar and grind them evenly to obtain a mixture A; the mass ratio of tetraaminobenzoquinone to sodium chloride is 1-2:20;

[0009] S2. Transferring the mixed material A to a ball mill, adding hydrochloric acid solution and then ball milling to obtain mixed material B;

[0010] S3, transferring the mixed material B into a sulfuric acid solution, heating and boiling, then filtering, collecting the precipitate, washing it with deionized water, and vacuum drying it at high temperature to obtain a powder;

[0011] The specific steps of step S4 are: transferring the obtained powder into anhydrous ethanol, stirring at a stirring speed of 300-400 rpm for 48-72 hours, filtering and vacuum drying at 60-70° C. for 6-7 hours to obtain an organic supramolecular conjugated polymer.

[0012] Furthermore, in step S1, the grinding time is 10-20 minutes.

[0013] Furthermore, in step S2, the ball milling process uses agate ball milling beads and a nylon ball milling jar, and then the nylon ball milling jar is fixed in a planetary ball mill for ball milling; the mass ratio of the agate ball milling beads to the mixed material 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.

[0014] Furthermore, in step S2, the ball milling process is performed at a rotation speed of 320-380 rpm, and the ball milling time is 10-15 minutes.

[0015] Furthermore, in step S2, the concentration of the hydrochloric acid solution is 10-12 mol / L; and in step S3, the concentration of the sulfuric acid solution is 0.02-0.03 mol / L.

[0016] Furthermore, the mass volume ratio of the tetraaminobenzoquinone, hydrochloric acid solution, and sulfuric acid solution is 1-4 g: 1-4 mL: 400-600 mL.

[0017] Furthermore, in step S3, the vacuum high-temperature drying temperature is 60-70° C. and the drying time is 5-7 hours.

[0018] Furthermore, in step S4, the material-liquid ratio of the powder to anhydrous ethanol is 1 to 3:1 in mg / mL.

[0019] The organic supramolecular conjugated polymer is prepared by the preparation method of the invention.

[0020] Furthermore, the organic supramolecular conjugated polymer is used in the preparation of potassium ion batteries.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1. This invention utilizes commercially available tetraaminobenzoquinone (TABQ) as a synthetic monomer and, through a self-polymerization strategy, produces an organic supramolecular conjugated polymer, namely polytetraaminobenzoquinone (pTABQ), an organic electrode material. By increasing the density of redox-active sites in the matrix, extending the π-conjugated molecular chain, and endowing the polymer with more complex intermolecular interactions, this material addresses the challenge of achieving a synergistic improvement in high capacity, high intrinsic conductivity, and high cycling stability when utilizing polymerization strategies to improve the energy storage potential of organic electrode materials.

[0023] 2. The preparation method of the present invention does not require high-temperature firing, and uses raw materials such as hydrochloric acid, sulfuric acid and anhydrous ethanol to prepare polytetraaminobenzoquinone organic electrode materials. It has outstanding advantages such as low raw materials, green process, high yield and easy large-scale production, while exhibiting excellent electrochemical properties. The proposed method provides a universal and efficient optimization path for the polymerization of organic small molecules, significantly improving the theoretical capacity, intrinsic conductivity and cycle stability of the material. Under the dual requirements of large-scale energy storage systems for high energy density and reliability, this type of organic electrode material with both fast kinetic response and durability shows broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 is an X-ray diffraction pattern of the polytetraaminobenzoquinone organic electrode material (pTABQ) prepared in Example 1, where 2θ refers to the diffraction angle;

[0025] Figure 2 is an infrared spectrum of the polytetraaminobenzoquinone organic electrode material (pTABQ) prepared in Example 1;

[0026] Figure 3 is a Raman spectrum of the polytetraaminobenzoquinone organic electrode material (pTABQ) prepared in Example 1;

[0027] Figure 4 is a molecular structure diagram of the polytetraaminobenzoquinone organic electrode material (pTABQ) prepared in Example 1;

[0028] Figure 5 This is the electron paramagnetic energy spectrum of the polytetraaminobenzoquinone organic electrode material (pTABQ) prepared in Example 1;

[0029] Figure 6 is a thermogravimetric diagram of the polytetraaminobenzoquinone organic electrode material (pTABQ) prepared in Example 1;

[0030] Figure 7This is a full spectrum comparison of the photoelectron spectra of the polytetraaminobenzoquinone organic electrode material (pTABQ) and tetraaminobenzoquinone (TABQ) prepared in Example 1;

[0031] Figure 8 This is the charge and discharge curve of a button-type potassium ion battery assembled with polytetraaminobenzoquinone organic electrode material (pTABQ) at a current density of 100 mA / g. DETAILED DESCRIPTION

[0032] In order to better understand the technical content of the present invention, specific examples are provided below to further illustrate the present invention.

[0033] Unless otherwise specified, the experimental methods used in the examples of the present invention are all conventional methods.

[0034] Unless otherwise specified, the materials, reagents, etc. used in the examples of the present invention can be obtained from commercial sources.

[0035] Example 1

[0036] A method for preparing an organic supramolecular conjugated polymer comprises the following steps:

[0037] S1. Add 1 g of tetraaminobenzoquinone and 20 g of sodium chloride to an agate mortar and grind thoroughly until a black mixture A with no obvious white powder is obtained;

[0038] S2. The black mixed material A obtained in step S1 was added to a nylon ball mill jar containing agate ball milling beads, wherein the mass ratio of the agate ball milling beads to the mixed material A was 40:1; the agate ball milling beads had particle sizes of 3 mm, 6 mm, and 8 mm, respectively, and the number ratio was 4:3:1; then 2 ml of a 12 mol / L concentrated hydrochloric acid solution was added, and the nylon ball mill jar was placed in a planetary ball mill and ball milled at a ball milling speed of 320 rpm for 12 minutes to obtain a reddish-brown mixed material B;

[0039] S3. The reddish-brown mixture B obtained in step S2 was transferred to a 1 L round-bottom flask. 500 ml of a 0.02 mol / L dilute sulfuric acid solution was added to the round-bottom flask and heated to a boil. The precipitate was collected by filtration, washed with deionized water three times, and then dried in an oven set at 70° C. under vacuum for 7 h to obtain a dark green powder.

[0040] S4. Take 200 mg of the dark green powder obtained in step S3, put it into 100 ml of anhydrous ethanol, stir it at a stirring speed of 300 rpm for 72 hours to perform solution polymerization, filter it, and then place the filtrate in an oven set at a temperature of 70° C. under a vacuum environment and dry it for 7 hours to obtain an organic supramolecular conjugated polymer, which is a polytetraaminobenzoquinone organic electrode material, denoted as pTABQ.

[0041] Figure 1 The X-ray diffraction pattern of the polytetraaminobenzoquinone organic electrode material (pTABQ) synthesized in the present invention is shown in FIG. Figure 1 As shown in Figure 3, the strong π peak near 28.3° corresponds to the π stacking feature, indicating that there is a strong intermolecular π force in this crystal plane direction.

[0042] like Figure 2 The infrared spectrum of -1 There are also multiple oscillation peaks nearby, which are derived from the interaction between amino group, amine hydrogen and carbonyl oxygen, indicating that there are abundant hydrogen bonds between the molecular chains of the polytetraaminobenzoquinone organic electrode material (pTABQ) synthesized in the present invention.

[0043] like Figure 3 As shown in the Raman spectrum, the polytetraaminobenzoquinone organic electrode material (pTABQ) synthesized in the present invention has a peak at 2800 cm -1 A broad characteristic peak appears at the pores, which is a typical feature of the hydrogen bond network. The ID / IG ratio is 0.81, indicating that the polytetraaminobenzoquinone organic electrode material (pTABQ) has a graphite-like layer structure.

[0044] like Figure 4 As shown in the molecular structure diagram, the polytetraaminobenzoquinone organic electrode material (pTABQ) synthesized by the present invention forms a molecular chain in a one-dimensional direction by removing the amino group connection. This long chain structure has a high degree of electron delocalization, which plays an important role in conductivity.

[0045] like Figure 5 As shown in the electron cis energy spectrum, the polytetraaminobenzoquinone organic electrode material (pTABQ) synthesized in the present invention has an obvious Gaussian signal, which means that pTABQ has potential high conductivity characteristics.

[0046] like Figure 6 As shown in the thermogravimetric diagram, the polytetraaminobenzoquinone organic electrode material (pTABQ) synthesized in the present invention begins to significantly thermally decompose at around 400°C due to its abundant intermolecular forces, and has very excellent thermal stability.

[0047] like Figure 7As shown, the polytetraaminobenzoquinone organic electrode material (pTABQ) synthesized by the present invention has a significantly lower nitrogen content than commercial tetraaminobenzoquinone (TABQ). This is because during the synthesis of pTABQ, TABQ is chained by removing amino groups, so the nitrogen content is relatively low.

[0048] Example 2

[0049] The organic supramolecular conjugated polymer (pTABQ) obtained in Example 1 was used to assemble a button-type potassium ion battery, as follows:

[0050] The polytetraaminobenzoquinone organic electrode material (pTABQ) prepared in Example 1 of the present invention was used as the negative electrode active material for potassium ion batteries, conductive carbon black was used as the conductive agent, and carboxymethyl cellulose was used as the binder. The active material, conductive agent, and binder were mixed in a mass ratio of 6:3:1, then added to deionized water to form a slurry, which was then evenly coated on copper foil. The electrode sheet was produced by punching the copper foil into a 10mm diameter disc. The punched electrode sheet had a mass loading of 0.8-1.2mg / cm -2 CR2016 coin cells were assembled in an argon glove box. Potassium metal sheets and glass fiber filter paper (GF / F) served as the counter electrode and separator, respectively. The potassium electrolyte consisted of 5 M KFSI dissolved in ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (solvent volume ratio of 1:1).

[0051] In this embodiment, the button-type potassium ion battery assembled with the organic supramolecular conjugated polymer and the potassium metal electrode sheet has a charge and discharge curve at a low current density of 100 mA / g as shown below: Figure 8 As shown: The polytetraaminobenzoquinone organic electrode material (pTABQ) exhibits a pair of significant redox peaks and exhibits high electrochemical activity with a capacity exceeding 400 mAh / g.

[0052] In button-type potassium-ion batteries assembled from organic supramolecular conjugated polymers and potassium metal electrode sheets, under long-term cycling at a high current density of 2000 mA / g, the polytetraaminobenzoquinone organic electrode material (pTABQ) benefits from its multiple redox active sites and high degree of electron delocalization, giving pTABQ high capacity and high conductivity characteristics. Therefore, it still exhibits a high capacity of over 220 mAh / g at a high current of 2000 mA / g. In addition, the rich intermolecular forces give pTABQ excellent cycling stability. After more than 500 cycles, the capacity retention rate is close to 100%.

[0053] Example 3

[0054] A method for preparing an organic supramolecular conjugated polymer, comprising the following steps:

[0055] S1. Add 2 g of tetraaminobenzoquinone and 20 g of sodium chloride to an agate mortar and grind thoroughly until a black mixture A with no obvious white powder is obtained;

[0056] S2. The black mixed material A obtained in step S1 was added to a nylon ball mill containing agate ball milling beads, wherein the mass ratio of the agate ball milling beads to the mixed material A was 50:1; the agate ball milling beads had particle sizes of 3 mm, 6 mm, and 8 mm, respectively, and the number ratio was 4:2:1; 2 ml of a 12 mol / L concentrated hydrochloric acid solution was then added, and the ball milling jar was placed in a planetary ball mill and ball milled at a speed of 350 rpm for 12 minutes to obtain a reddish-brown mixed material B;

[0057] S3. The reddish-brown mixture B obtained in step S2 was transferred to a 1 L round-bottom flask. 500 ml of a 0.03 mol / L dilute sulfuric acid solution was added to the round-bottom flask and heated to a boil. The precipitate was collected by filtration, washed three times with deionized water and ethanol, and then dried in a vacuum oven at 60° C. for 5 h to obtain a dark green powder.

[0058] S4. Take 200 mg of the dark green powder obtained in step S3, put it into 100 ml of anhydrous ethanol, stir it at a stirring speed of 350 rpm for 60 hours to perform solution polymerization, filter it, and then place the filtrate in an oven set at a temperature of 70° C. under a vacuum environment and dry it for 6 hours to obtain an organic supramolecular conjugated polymer, which is a polytetraaminobenzoquinone organic electrode material, denoted as pTABQ.

[0059] Example 4

[0060] A method for preparing an organic supramolecular conjugated polymer, comprising the following steps:

[0061] S1. Add 1 g of tetraaminobenzoquinone and 20 g of sodium chloride to an agate mortar and grind thoroughly until a black mixture A with no obvious white powder is obtained;

[0062] S2. The black mixed material A obtained in step S1 was added to a nylon ball mill jar containing agate ball milling beads, wherein the mass ratio of the agate ball milling beads to the mixed material A was 30:1; the agate ball milling beads had particle sizes of 3 mm, 6 mm, and 8 mm, respectively, and the number ratio was 2:3:1; 2 ml of a 12 mol / L concentrated hydrochloric acid solution was then added, and the nylon ball mill jar was placed in a planetary ball mill and ball milled at a ball milling speed of 360 rpm for 15 minutes to obtain a reddish-brown mixed material B;

[0063] S3. The reddish-brown mixture B obtained in step S2 was transferred to a 1 L round-bottom flask. 500 ml of a 0.03 mol / L dilute sulfuric acid solution was added to the round-bottom flask and heated to a boil. The precipitate was collected by filtration, washed three times with deionized water and ethanol, and then dried in a vacuum oven at 70° C. for 5 h to obtain a dark green powder.

[0064] S4. Take 200 mg of the dark green powder obtained in step S3, put it into 100 ml of anhydrous ethanol, stir it at a stirring speed of 400 rpm for 48 hours to perform solution polymerization, filter it, and then place the filtrate in an oven set at a temperature of 60° C. under a vacuum environment and dry it for 7 hours to obtain a polytetraaminobenzoquinone organic electrode material, which is an organic supramolecular conjugated polymer, denoted as pTABQ.

[0065] Example 5

[0066] A method for preparing an organic supramolecular conjugated polymer comprises the following steps:

[0067] S1. Add 1 g of tetraaminobenzoquinone and 20 g of sodium chloride to an agate mortar and grind thoroughly until a black mixture with no obvious white powder is obtained;

[0068] S2. The black mixture obtained in step S1 was added to a nylon ball mill jar containing agate ball milling beads, wherein the mass ratio of the agate ball milling beads to the mixture A was 40:1; the agate ball milling beads had particle sizes of 3 mm, 6 mm, and 8 mm, respectively, and the number ratio was 3:2:1; then 2 ml of a 12 mol / L concentrated hydrochloric acid solution was added, and the nylon ball mill jar was placed in a planetary ball mill and ball milled at a ball milling speed of 380 rpm for 10 minutes to obtain a reddish-brown mixture B;

[0069] S3. The reddish-brown mixture B obtained in step S2 was transferred to a 1 L round-bottom flask. 500 ml of a 0.02 mol / L dilute sulfuric acid solution was added to the round-bottom flask and heated to a boil. The precipitate was collected by filtration, washed three times with deionized water and ethanol, and then dried in a vacuum oven at 70° C. for 6 h to obtain a dark green powder.

[0070] S4. Take 200 mg of the dark green powder obtained in step S3, put it into 100 ml of anhydrous ethanol, stir it at a stirring speed of 400 rpm for 48 hours to perform solution polymerization, filter it, and then place the filtrate in an oven set at a temperature of 60° C. under a vacuum environment and dry it for 7 hours to obtain an organic supramolecular conjugated polymer, which is a polytetraaminobenzoquinone organic electrode material, denoted as pTABQ.

[0071] Comparative Example 1

[0072] The present invention is based on Example 1, except that the anhydrous ethanol in step S4 is replaced with acetonitrile, and the rest is consistent with Example 1.

[0073] The preparation method of an organic supramolecular conjugated polymer in this comparative example comprises the following steps:

[0074] S1. Add 1 g of tetraaminobenzoquinone and 20 g of sodium chloride to an agate mortar and grind thoroughly until a black mixture A with no obvious white powder is obtained;

[0075] S2. The black mixed material A obtained in step S1 was added to a nylon ball mill jar containing agate ball milling beads, wherein the mass ratio of the agate ball milling beads to the mixed material A was 40:1; the agate ball milling beads had particle sizes of 3 mm, 6 mm, and 8 mm, respectively, and the number ratio was 4:3:1; then 2 ml of a 12 mol / L concentrated hydrochloric acid solution was added, and the nylon ball mill jar was placed in a planetary ball mill and ball milled at a ball milling speed of 320 rpm for 12 minutes to obtain a reddish-brown mixed material B;

[0076] S3. The reddish-brown mixture B obtained in step S2 was transferred to a 1 L round-bottom flask. 500 ml of a 0.02 mol / L dilute sulfuric acid solution was added to the round-bottom flask and heated to a boil. The precipitate was collected by filtration, washed with deionized water three times, and then dried in an oven set at 70° C. under vacuum for 7 h to obtain a dark green powder.

[0077] S4. Take 200 mg of the dark green powder obtained in step S3, put it into 100 ml of acetonitrile, stir it at a stirring speed of 300 rpm for 72 hours to perform solution polymerization, filter it, and then place the filtrate in a vacuum oven set at a temperature of 70°C for 7 hours to obtain an organic supramolecular conjugated polymer, which is a polytetraaminobenzoquinone organic electrode material, denoted as pTABQ.

[0078] 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%, which was lower in performance than the polytetraaminobenzoquinone organic electrode material prepared in Example 1.

[0079] Comparative Example 2

[0080] On the basis of Example 1, the present invention replaces the anhydrous ethanol in step S4 with an ethanol solution with a volume concentration of 70%, and the rest remains the same as Example 1.

[0081] The preparation method of an organic supramolecular conjugated polymer in this comparative example comprises the following steps:

[0082] S1. Add 1 g of tetraaminobenzoquinone and 20 g of sodium chloride to an agate mortar and grind thoroughly until a black mixture A with no obvious white powder is obtained;

[0083] S2. The black mixed material A obtained in step S1 was added to a nylon ball mill jar containing agate ball milling beads, wherein the mass ratio of the agate ball milling beads to the mixed material A was 40:1; the agate ball milling beads had particle sizes of 3 mm, 6 mm, and 8 mm, respectively, and the number ratio was 4:3:1; then 2 ml of a 12 mol / L concentrated hydrochloric acid solution was added, and the nylon ball mill jar was placed in a planetary ball mill and ball milled at a ball milling speed of 320 rpm for 12 minutes to obtain a reddish-brown mixed material B;

[0084] S3. The reddish-brown mixture B obtained in step S2 was transferred to a 1 L round-bottom flask. 500 ml of a 0.02 mol / L dilute sulfuric acid solution was added to the round-bottom flask and heated to a boil. The precipitate was collected by filtration, washed with deionized water three times, and then dried in an oven set at 70° C. under vacuum for 7 h to obtain a dark green powder.

[0085] S4. Take 200 mg of the dark green powder obtained in step S3, put it into 100 ml of 70% ethanol solution, stir it at a stirring speed of 300 rpm for 72 hours to perform solution polymerization, filter it, and then place the filtrate in a vacuum oven set at a temperature of 70° C. and dry it for 7 hours to obtain an organic supramolecular conjugated polymer, which is a polytetraaminobenzoquinone organic electrode material, denoted as pTABQ.

[0086] 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 a long cycle 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%, which was lower than the performance effect of the polytetraaminobenzoquinone organic electrode material prepared in Example 1.

[0087] The results of Comparative Examples 1 and 2 above show that the polytetraaminobenzoquinone organic electrode material prepared by the present invention using hydrochloric acid, sulfuric acid and anhydrous ethanol as raw materials has good performance.

[0088] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing an organic supramolecular conjugated polymer, characterized in that: The following steps are involved: S1. Add tetraaminobenzoquinone and sodium chloride into a mortar and grind them evenly to obtain a mixture A; the mass ratio of tetraaminobenzoquinone to sodium chloride is 1-2:20; S2. Transferring the mixed material A to a ball mill, adding hydrochloric acid solution and then ball milling to obtain mixed material B; S3, transferring the mixed material B into a sulfuric acid solution, heating and boiling, then filtering, collecting the precipitate, washing it with deionized water, and vacuum drying it at high temperature to obtain a powder; S4. Transfer the obtained powder into anhydrous ethanol, wherein the solid-liquid ratio of the powder to anhydrous ethanol is 1-3:1 in mg / mL, and stir at a stirring speed of 300-400 rpm for 48-72 hours. After filtering, vacuum dry at 60-70° C. for 6-7 hours to obtain an organic supramolecular conjugated polymer.

2. The method for preparing an organic supramolecular conjugated polymer according to claim 1, wherein In step S2, the ball milling process uses agate ball milling beads and a nylon ball milling jar, and then the nylon ball milling jar is fixed in a planetary ball mill for ball milling; the mass ratio of the agate ball milling beads to the mixed material 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 method for preparing an organic supramolecular conjugated polymer according to claim 1, wherein In step S2, the ball milling process is performed at a rotation speed of 320-380 rpm and a ball milling time of 10-15 minutes.

4. The method for preparing an 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 method for preparing an organic supramolecular conjugated polymer according to claim 1, wherein: 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 method for preparing an organic supramolecular conjugated polymer according to claim 1, wherein: In step S3, the vacuum high-temperature drying temperature is 60-70° C. and the drying time is 5-7 hours.

7. An organic supramolecular conjugated polymer obtained by the preparation method according to any one of claims 1 to 6.

8. The organic supramolecular conjugated polymer according to claim 7, characterized in that The organic supramolecular conjugated polymer is used in the preparation of potassium ion batteries.

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