Preparation method and application of a chain amide organic polymer material for aqueous ammonium ion battery

Abstract

The application relates to a preparation method and application of a chain amide organic polymer electrode material for an aqueous ammonium ion battery, and belongs to the technical field of energy storage materials. Tetraamino-p-benzoquinone is subjected to nucleophilic substitution with potassium phthalimide to obtain an intermediate product tetra(phthalimide)-benzoquinone, then through an aminolysis reaction, tetraaminobenzoquinone (TABQ) is obtained, and then through nucleophilic reaction of carbonyl carbon atoms in 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and nitrogen atoms of the TABQ, a chain organic polymer material is prepared. The acid anhydride monomer is combined with the amine monomer into the chain amide organic polymer material, the structural stability of the material is increased, and the improvement of the cycle stability of the battery is facilitated.

Description

Technical Field

[0001] This invention belongs to the field of energy storage materials technology, and relates to a method for preparing and applying a chain-like amide organic polymer material for aqueous ammonium-ion batteries. Background Technology

[0002] In recent years, with the depletion of fossil fuels and the increasing severity of environmental pollution, the research and development of new energy storage materials has received increasing attention. Existing lithium-ion batteries suffer from drawbacks such as lithium metal shortages and the toxicity, flammability, and explosiveness of organic electrolytes. Aqueous ammonium-ion batteries, using aqueous solutions as electrolytes, offer advantages such as environmental friendliness, safety, and low cost, showing promising development prospects. However, the limited electrochemical performance of aqueous ammonium-ion battery energy storage materials restricts their commercial development, making it one of the current hot research topics. As the center of the battery's redox reaction, electrode materials are responsible for both ion and electron transfer and separation, largely determining the overall battery performance. Therefore, the exploration of electrode materials for aqueous ammonium-ion batteries is crucial. Organic materials often possess a large number of nitrogen and oxygen functional groups, capable of reacting with NH4+... 4+ Hydrogen bonds are formed, thereby achieving NH 4+ Storage is a promising area for ammonium storage materials. However, small organic molecules are prone to dissolution, structural instability, and aggregation and stacking, which greatly affects the performance of electrode materials. Summary of the Invention

[0003] The purpose of this invention is to utilize the nucleophilic reaction between the carbonyl carbon atom in 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and the nitrogen atom in TABQ to prepare chain-like amide-based organic polymer materials, thereby improving the problem of poor material cycling stability caused by the instability of small organic molecules, their tendency to aggregate and stack.

[0004] The technical solution adopted in this invention is:

[0005] A method for preparing a chain-like amide-based organic polymer material for aqueous ammonium-ion batteries includes the following steps:

[0006] 1) Preparation of tetra(phthalimide)-benzoquinone: Under N2 atmosphere, 5.0 g of tetrachloro-p-benzoquinone, 15.0 g of potassium phthalimide, and 50.0 mL of acetonitrile were placed in a round-bottom flask. The mixture was repeatedly evacuated and purged with N2 using a double-row tube, and heated in an oil bath. After cooling to room temperature, the product was filtered and washed three times with 100 mL of N,N-dimethylformamide at 100 °C and 100 mL of deionized water at 100 °C until the filtrate was colorless. The product was then suspended in 100 mL of anhydrous ethanol and heated to boiling. The mixture was then vacuum filtered and dried overnight in a vacuum drying oven at 60 °C to obtain brownish-yellow tetra(phthalimide)-benzoquinone TPQ.

[0007] 2) Synthesis of TABQ: 4.71 g of TPQ synthesized in step 1) was transferred to a round-bottom flask. 100 mL of 80.0 wt% hydrazine hydrate was added to the round-bottom flask. After stirring at room temperature, the mixture was heated in an oil bath and then filtered under vacuum. The mixture was dried overnight to obtain purple-black tetraaminobenzoquinone TABQ.

[0008] 3) Preparation of chain amide organic polymer materials: 0.20 g of 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and 0.084 g of TABQ synthesized in step 2) were placed in a solvent pressure-resistant tube, and 0.044 g of zinc acetate catalyst and 2 g of imidazole solvent were added. The solvent pressure-resistant tube was repeatedly evacuated and purged with N2 three times using a double-row tube. Then, the solvent pressure-resistant tube was heated in an oil bath under N2 atmosphere. After cooling to room temperature, the product was washed with a large amount of deionized water and tetrahydrofuran, and then vacuum dried overnight to obtain the product.

[0009] Furthermore, in the above preparation method, step 1), the conditions for the oil bath heating reaction are: 80°C oil bath heating and stirring for 12 hours.

[0010] Furthermore, in the above preparation method, step 2), the stirring time is 2 hours.

[0011] Furthermore, in the above preparation method, step 2), the conditions for the oil bath heating reaction are: heating in an oil bath at 65°C for 2 hours.

[0012] Furthermore, in the above preparation method, step 3), the conditions for the oil bath heating reaction are: first, heat in an oil bath at 110°C for 2 hours, and then raise the temperature to 140°C for 2 days.

[0013] The application of the chain-like amide organic polymer materials prepared by any of the above preparation methods as electrode materials for aqueous ammonium ion batteries.

[0014] Furthermore, the above application is carried out as follows: a chain amide organic polymer material, polyvinylidene fluoride, superconducting carbon black and N-methylpyrrolidone are mixed, thoroughly ground and then uniformly coated onto the surface of a flexible carbon cloth current collector to obtain a battery electrode.

[0015] Furthermore, in the above applications, the mass ratio of chain amide organic polymer materials: polyvinylidene fluoride: superconducting carbon black is 8:1:1.

[0016] The beneficial effects of this invention are as follows:

[0017] 1. This invention involves nucleophilic substitution of tetraamino-p-benzoquinone with potassium phthalimide to obtain the intermediate tetra(phthalimide)-benzoquinone, followed by aminolysis to obtain tetraaminobenzoquinone (TABQ). Then, a chain-like amide-based organic polymer material is prepared by utilizing the nucleophilic reaction between the carbonyl carbon atom of 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and the nitrogen atom of TABQ. Small organic molecules suffer from easy solubility, structural instability, and a tendency to aggregate and stack, which significantly impacts the performance of electrode materials. This invention combines anhydride monomers with amine monomers to form a chain-like amide-based organic polymer material, increasing the structural stability of the material and improving battery cycle stability.

[0018] 2. The chain-like amide organic polymer material synthesized in this invention is a long-chain macromolecule. This active substance is more stable, which is beneficial for improving cycle stability. Furthermore, the chain structure exposes more active sites, which is beneficial for NH4+. + Storage. Attached Figure Description

[0019] Figure 1 These are low-magnification (a) and high-magnification (b) scanning electron microscope images of the chain amide organic polymer material prepared in Example 1.

[0020] Figure 2 This is a cyclic voltammetry curve of the chain amide organic polymer battery electrode prepared in Example 2 at a scan rate of 5 mV / s.

[0021] Figure 3 The chain-like amide-based organic polymer battery electrode prepared in Example 2 is in 2Ag -1 Charge-discharge curves at current density.

[0022] Figure 4 The chain-like amide-based organic polymer battery electrode prepared in Example 2 was tested at 20 Ag. -1 Charge-discharge curves at current density.

[0023] Figure 5 The chain-like amide-based organic polymer battery electrode prepared in Example 2 was tested at 5Ag. -1 Cyclic curves after 5000 charge-discharge cycles at current density. Detailed Implementation

[0024] Example 1

[0025] Preparation of chain-like amide-based organic polymer materials for aqueous ammonium-ion batteries:

[0026] 1) Preparation of tetra(phthalimide)-benzoquinone: Under N2 atmosphere, 5.0 g of tetrachloro-p-benzoquinone, 15.0 g of potassium phthalimide, and 50.0 mL of acetonitrile were placed in a round-bottom flask. The flask was repeatedly evacuated and purged with N2 using a double-row tube three times. The temperature was then raised to 80 °C and heated in an oil bath with stirring for 12 h. After cooling to room temperature, the product was filtered and washed three times with 100 mL of 100 °C N,N-dimethylformamide (DMF) and 100 mL of 100 °C deionized water until the filtrate was colorless. The product was then suspended in 100 mL of anhydrous ethanol and heated to boiling. The product was then vacuum filtered and dried overnight in a vacuum drying oven at 60 °C to obtain brownish-yellow tetra(phthalimide)-benzoquinone (TPQ).

[0027] 2) Synthesis of TABQ: 4.71 g of TPQ synthesized in step 1) was transferred to a round-bottom flask. 100 mL of 80.0 wt% hydrazine hydrate was added to the round-bottom flask. After stirring at room temperature for 2 h, the mixture was heated in an oil bath at 65 °C for 2 h and then vacuum filtered. The mixture was dried overnight to obtain purple-black tetraaminobenzoquinone (TABQ).

[0028] 3) Preparation of chain amide organic polymer materials: 0.20 g of 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and 0.084 g of TABQ synthesized in step 2) were placed in a solvent pressure-resistant tube, and 0.044 g of zinc acetate catalyst and 2 g of imidazole solvent were added. The solvent pressure-resistant tube was repeatedly evacuated and purged with N2 using a double-row tube. Then, the solvent pressure-resistant tube was heated in an oil bath at 110 °C for 2 h under N2 atmosphere, and then the temperature was raised to 140 °C for 2 days. After cooling to room temperature, the product was washed with a large amount of deionized water and tetrahydrofuran, and then vacuum dried overnight to obtain the product.

[0029] Figure 1 These are low-magnification (a) and high-magnification (b) scanning electron microscope images of the chain amide organic polymer material prepared in step 3) of Example 1. Figure 1 The microstructure of the prepared chain amide organic polymer material is visible.

[0030] Example 2

[0031] Chain-like amide-based organic polymer materials for aqueous ammonium-ion batteries and their preparation as electrode materials for aqueous ammonium-ion batteries:

[0032] 1) Preparation of tetra(phthalimide)-benzoquinone: Under N2 atmosphere, 5.0 g of tetrachloro-p-benzoquinone, 15.0 g of potassium phthalimide, and 50.0 mL of acetonitrile were placed in a round-bottom flask. The flask was repeatedly evacuated and purged with N2 using a double-row tube three times. The temperature was then raised to 80 °C and heated in an oil bath with stirring for 12 h. After cooling to room temperature, the product was filtered and washed three times with 100 mL of 100 °C N,N-dimethylformamide (DMF) and 100 mL of 100 °C deionized water until the filtrate was colorless. The product was then suspended in 100 mL of anhydrous ethanol and heated to boiling. The product was then vacuum filtered and dried overnight in a vacuum drying oven at 60 °C to obtain brownish-yellow tetra(phthalimide)-benzoquinone (TPQ).

[0033] 2) Synthesis of TABQ: 4.71 g of TPQ synthesized in step 1) was transferred to a round-bottom flask. 100 mL of 80.0 wt% hydrazine hydrate was added to the round-bottom flask. After stirring at room temperature for 2 h, the mixture was heated in an oil bath at 65 °C for 2 h and then vacuum filtered. The mixture was dried overnight to obtain purple-black tetraaminobenzoquinone (TABQ).

[0034] 3) Preparation of chain amide organic polymer materials: 0.20 g of 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and 0.084 g of TABQ synthesized in step 2) were placed in a solvent pressure-resistant tube, and 0.044 g of zinc acetate catalyst and 2 g of imidazole solvent were added. The solvent pressure-resistant tube was repeatedly evacuated and purged with N2 using a double-row tube. Then, the solvent pressure-resistant tube was heated in an oil bath at 110 °C for 2 h under N2 atmosphere, and then the temperature was raised to 140 °C for 2 days. After cooling to room temperature, the product was washed with a large amount of deionized water and tetrahydrofuran, and then vacuum dried overnight to obtain the product.

[0035] 4) Electrode preparation: A mixture of chain amide organic polymer material, polyvinylidene fluoride and superconducting carbon black with N-methylpyrrolidone in a mass ratio of 8:1:1 was thoroughly ground and then uniformly coated onto the surface of a flexible carbon cloth current collector to obtain a battery electrode. After drying, the electrode was weighed and the active material content was 2.10 mg.

[0036] Figure 2 These are the cyclic voltammetry curves of the chain-like amide-based organic polymer battery electrode prepared in step 4) of Example 2, at a scan rate of 5 mV / s. Figure 2 The voltage range of this material can be determined to be -1 to 0.2V.

[0037] Figure 3 The chain-like amide-based organic polymer battery electrode prepared in step 4 of Example 2 is in 2Ag -1 Charge-discharge curves at current density. Figure 3 It can be seen that in 0.5M (NH4)2SO4, 2Ag -1 At a current density of , the discharge capacity of the chain amide organic polymer material is 66.44 mAh g.-1 .

[0038] Figure 4 The chain-like amide-based organic polymer battery electrode prepared in step 4 of Example 2 is subjected to 20Ag -1 Charge-discharge curves at current density. Figure 4 It can be seen that in 0.5M (NH4)2SO4, 20Ag -1 The discharge specific capacity at the current density is 40.24 mAh g. -1 The charging specific capacity is 39.28mAh g. -1 The Coulomb efficiency is 102.44%.

[0039] Figure 5 The chain-like amide-based organic polymer battery electrode prepared in step 4 of Example 2 is subjected to 5Ag -1 Cycling curves after 5000 charge-discharge cycles at current density. In 0.5M (NH4)2SO4, 5Ag -1 The discharge specific capacity in the second cycle at the current density is 60.85 mAh g. -1 After 50 cycles, the capacity decreased to 52.51 mAh g. -1 It then stabilized. After 5000 charge-discharge cycles, the capacity remained at 42.93 mAh g. -1 It exhibits a capacity retention rate of 70.55% and excellent cycle stability.

Claims

1. The application of a chain-like amide-based organic polymer material as an electrode material for aqueous ammonium-ion batteries, characterized in that, The preparation method of the chain-like amide organic polymer material includes the following steps: 1) Preparation of tetra(phthalimide)-benzoquinone: Under N2 atmosphere, 5.0 g of tetrachloro-p-benzoquinone, 15.0 g of potassium phthalimide, and 50.0 mL of acetonitrile were placed in a round-bottom flask. The mixture was repeatedly evacuated and purged with N2 using a double-row tube, and heated in an oil bath. After cooling to room temperature, the product was filtered and washed three times with 100 mL of N,N-dimethylformamide at 100 °C and 100 mL of deionized water at 100 °C until the filtrate was colorless. The product was then suspended in 100 mL of anhydrous ethanol and heated to boiling. After vacuum filtration, the product was dried overnight in a vacuum drying oven at 60 °C to obtain brownish-yellow tetra(phthalimide)-benzoquinone TPQ. 2) Synthesis of TABQ: 4.71 g of TPQ synthesized in step 1) was transferred to a round-bottom flask. 100 mL of 80.0 wt% hydrazine hydrate was added to the round-bottom flask. After stirring at room temperature, the mixture was heated in an oil bath and then filtered under vacuum. The mixture was dried overnight to obtain purple-black tetraaminobenzoquinone TABQ. 3) Preparation of chain amide organic polymer materials: 0.20 g of 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and 0.084 g of TABQ synthesized in step 2) were placed in a solvent pressure-resistant tube, and 0.044 g of zinc acetate catalyst and 2 g of imidazole solvent were added. The solvent pressure-resistant tube was repeatedly evacuated and purged with N2 three times using a double-row tube. Then, the solvent pressure-resistant tube was heated in an oil bath under N2 atmosphere. After cooling to room temperature, the product was washed with a large amount of deionized water and tetrahydrofuran, and then vacuum dried overnight to obtain the product.

2. The application according to claim 1, characterized in that, In step 1), the conditions for the oil bath heating reaction are: 80 °C oil bath heating and stirring for 12 h.

3. The application according to claim 1, characterized in that, In step 2), the stirring time is 2 hours.

4. The application according to claim 1, characterized in that, In step 2), the conditions for the oil bath heating reaction are: heating in an oil bath at 65 ℃ for 2 h.

5. The application according to claim 1, characterized in that, In step 3), the conditions for the oil bath heating reaction are: first heat in an oil bath at 110 ℃ for 2 h, then raise the temperature to 140 ℃ and react for 2 days.

6. The application according to claim 1, characterized in that, The method is as follows: a chain amide organic polymer material, polyvinylidene fluoride, superconducting carbon black and N-methylpyrrolidone are mixed, ground thoroughly and then uniformly coated onto the surface of a flexible carbon cloth current collector to obtain a battery electrode.

7. The application according to claim 6, characterized in that, By mass ratio, the ratio of chain amide organic polymer materials to polyvinylidene fluoride to superconducting carbon black is 8:1:1.

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