Application of organic amide polymer material PAAT as aqueous ammonium ion battery electrode

Abstract

The invention belongs to the technical field of energy storage materials, and particularly relates to application of an organic amide polymer material PAAT as an aqueous ammonium ion battery electrode. According to the invention, 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA) and 2, 4, 6-tri (4-aminophenyl)-1, 3, 5-triazine (TAPT) are subjected to an amide condensation polymerization reaction, and a chain-like organic polymer material PAAT is prepared. According to the invention, the anhydride monomer and the amine monomer are combined to form the chain-like organic polymer material PAAT, so that the structural stability of the material is improved, and the PAAT is used as an aqueous ammonium ion battery electrode to facilitate the improvement of the electrochemical performance of the battery.

Description

Technical Field

[0001] The present invention belongs to the technical field of energy storage materials, and particularly relates to the application of an organic amide polymer material PAAT as an electrode for an aqueous ammonium ion battery. Background Art

[0002] In recent years, with the increasingly urgent need for energy structure transformation and sustainable development, the research on new electrochemical energy storage technologies has received much attention. Compared with the resource limitations and safety risks faced by traditional lithium-ion batteries, the aqueous ammonium ion energy storage system with an aqueous solution as the electrolyte exhibits unique application advantages, and its intrinsically safe and eco-friendly characteristics provide a new direction for large-scale energy storage. However, this technical system still faces a key bottleneck in practical applications - the charge storage efficiency and cycle stability of the electrode material need to be improved urgently, which has become the core problem restricting its industrialization process. At the energy storage mechanism level, as the carrier of ion / electron transport, the interfacial properties and structural stability of the electrode material directly affect the comprehensive performance of the device. Organic electrode materials have rich polar functional groups and can form hydrogen bond interactions with ammonium ions, showing ideal charge storage potential. However, current research shows that small molecule organic active substances are prone to dissolve and lose in the electrolyte, and the uncontrollable stacking caused by intermolecular forces will significantly reduce the utilization rate of effective active sites, which poses an important challenge for the development of high-performance electrode materials. Summary of the Invention

[0003] The present invention uses the nucleophilic reaction of the carbonyl carbon atoms in 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) with the atoms of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) to prepare a chain-like organic amide polymer material PAAT, so as to improve the problems of low material capacity and poor performance caused by the unstable structure, easy aggregation and stacking of organic small molecules.

[0004] To achieve the above object, the present invention provides an application of an organic amide polymer material PAAT as an electrode for an aqueous ammonium ion battery.

[0005] The technical solution adopted by the present invention is as follows:

[0006] An application of an organic amide polymer material PAAT as an electrode for an aqueous ammonium ion battery.

[0007] Further, for the above application, the method is as follows: Mix the organic amide polymer material PAAT with polyvinylidene fluoride, superconducting carbon black and N-methylpyrrolidone, and after fully grinding, evenly coat it on the surface of a functionalized flexible carbon cloth current collector material to obtain a battery electrode.

[0008] Furthermore, for the above application, by mass ratio, PAAT: polyvinylidene fluoride: superconducting carbon black = 7:2:1.

[0009] Furthermore, in the above application, the dosage of N-methylpyrrolidone is just enough to infiltrate PAAT, polyvinylidene fluoride and superconducting carbon black powder to form a slurry with them.

[0010] Further, in the above application, the preparation method of the organic amide polymer material PAAT includes the following steps: Put 3,4,9,10-perylene tetracarboxylic dianhydride and 2,4,6-tris(4-aminophenyl)-1,3,5-triazine into a solvent pressure-resistant tube, and add the catalyst zinc acetate and the solvent N-methylpyrrolidone. Under N 2 atmosphere, heat the solvent pressure-resistant tube in an oil bath at 110°C for 2 h, then raise the temperature to 140°C and react for 2 days. After cooling to room temperature, wash the product with a large amount of deionized water and tetrahydrofuran until the filtrate is colorless, and dry it overnight under vacuum to obtain the product organic amide polymer material PAAT.

[0011] Further, in the preparation method of the above-mentioned organic amide polymer material PAAT, by molar ratio, 3,4,9,10-perylene tetracarboxylic dianhydride: 2,4,6-tris(4-aminophenyl)-1,3,5-triazine: zinc acetate = 5:5:2.

[0012] Further, in the preparation method of the above-mentioned organic amide polymer material PAAT, the dosage of the N-methylpyrrolidone is to immerse 3,4,9,10-perylene tetracarboxylic dianhydride, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine and zinc acetate powder.

[0013] Further, in the preparation method of the above-mentioned organic amide polymer material PAAT, the N 2 atmosphere is obtained by repeatedly evacuating and introducing N three times using a double-tube. 2 .

[0014] The beneficial effects of the present invention are as follows:

[0015] 1. The present invention prepares a chain-like organic polymer material PAAT by using the nucleophilic reaction of the carbonyl carbon atom in 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) with the nitrogen atom in 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT).

[0016] 2. The present invention solves the problems that organic small molecules are easy to dissolve and have unstable structures, and are prone to agglomeration and stacking, which greatly affects the performance of electrode materials.

[0017] 3. The present invention combines acid anhydride monomers and amine monomers to form a long-chain organic polymer material, increasing the structural stability of the material and being beneficial to the improvement of the battery cycle stability performance. Description of the Drawings

[0018] Figure 1 It is the infrared spectrum of PAAT synthesized in Example 1.

[0019] Figure 2 It is the cyclic voltammogram of the PAAT battery electrode prepared in Example 2 at a scan rate of 5 mV / s.

[0020] Figure 3 It is the charge-discharge curve of the PAAT battery electrode prepared in Example 3 at a current density of 1 A g -1 of.

[0021] Figure 4 It is the charge-discharge curve of the PAAT battery electrode prepared in Example 4 at a current density of 20 A g -1 of.

[0022] Figure 5 It is the charge-discharge cycle curve of the PAAT battery electrode prepared in Example 5 at a current density of 10 A g -1 for 1000 charge-discharge cycles.

[0023] Figure 6 It is a physical picture of the button ammonium ion battery prepared in Example 6 powering an LED lamp.

[0024] Figure 7 It is the PAAT synthesis reaction formula. Specific implementation mode

[0025] Example 1

[0026] A preparation method of an organic amide polymer material PAAT, comprising the following steps:

[0027] Synthesis of PAAT (as Figure 6 ): Put 0.20 g of 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) and 0.18 g of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) into a solvent pressure-resistant tube, and add 0.044 g of zinc acetate and 50 mL of N-methylpyrrolidone (NMP). Use a double-tube to evacuate and fill the solvent pressure-resistant tube with N 2 three times repeatedly, and then 2 under N atmosphere, heat the solvent pressure-resistant tube in an oil bath at 110 °C for 2 h, then raise the temperature to 140 °C and react for 2 days. After cooling to room temperature, wash the product with a large amount of deionized water and tetrahydrofuran until the filtrate is colorless, and dry it overnight under vacuum to obtain the product organic amide polymer material PAAT.

[0028] Figure 1 is the infrared spectrum of PAAT synthesized in Example 1. It can be seen from the infrared spectrum that the absorption peak of the amide structure of PAAT proves successful synthesis.

[0029] Example 2

[0030] A method for preparing a PAAT battery electrode for an aqueous ammonium ion battery comprises the following steps:

[0031] 1) Synthesis of PAAT: 0.20 g of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and 0.18 g of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) were placed in a solvent pressure tube, and 0.044 g of zinc acetate and 50 mL of N-methylpyrrolidone (NMP) were added. The solvent pressure tube was repeatedly evacuated three times using a double-row tube and N was passed through. 2 , then in N 2 The solvent pressure tube was heated in an oil bath at 110°C for 2 hours under an atmosphere, and then heated to 140°C for reaction for 2 days. After cooling to room temperature, the product was washed with a large amount of deionized water and tetrahydrofuran until the filtrate was colorless, and vacuum dried overnight to obtain the product organic amide polymer material PAAT.

[0032] 2) PAAT was mixed with polyvinylidene fluoride, superconducting carbon black and an appropriate amount of N-methylpyrrolidone (just enough to wet the material powder), and after being fully ground, it was evenly coated on the surface of the flexible carbon cloth current collector material to obtain a PAAT battery electrode; the mass ratio of PAAT: polyvinylidene fluoride: superconducting carbon black was 7:2:1. After drying and weighing, the mass of PAAT active material was 1.72 mg.

[0033] Figure 2 The electrode prepared in Example 2 is 5mV s -1 Cyclic voltammetry curve at the scan rate. Figure 2 The PAAT voltage range can be determined to be -1.1 to 0.2V.

[0034] Example 3

[0035] A method for preparing a PAAT battery electrode for an aqueous ammonium ion battery comprises the following steps:

[0036] 1) Synthesis of PAAT: 0.20 g of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and 0.18 g of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) were placed in a solvent pressure tube, and 0.044 g of zinc acetate and 50 mL of N-methylpyrrolidone (NMP) were added. The solvent pressure tube was repeatedly evacuated three times using a double-row tube and N was passed through. 2 , then in N 2 The solvent pressure tube was heated in an oil bath at 110°C for 2 hours under an atmosphere, and then heated to 140°C for reaction for 2 days. After cooling to room temperature, the product was washed with a large amount of deionized water and tetrahydrofuran until the filtrate was colorless, and vacuum dried overnight to obtain the product organic amide polymer material PAAT.

[0037] 2) PAAT was mixed with polyvinylidene fluoride, superconducting carbon black and an appropriate amount of N-methylpyrrolidone (just enough to wet the material powder), and after thorough grinding, it was evenly coated on the surface of the flexible carbon cloth current collector material to obtain the PAAT battery electrode; by mass ratio, PAAT: polyvinylidene fluoride: superconducting carbon black = 7:2:1. After drying, it was weighed, and the mass of the PAAT active material was 1.69 mg.

[0038] Figure 3 It is the charge-discharge curve of the electrode prepared in Example 3 at a current density of 1 Ag -1 From the charge-discharge curve, it can be seen that the capacity of PAAT can reach 63.08 mAh g -1 at a current density of 1 A g -1 .

[0039] Example 4

[0040] A preparation method of a PAAT battery electrode for an aqueous ammonium ion battery includes the following steps:

[0041] 1) Synthesis of PAAT: 0.20 g of 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) and 0.18 g of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) were placed in a solvent-resistant pressure tube, and 0.044 g of zinc acetate and 50 mL of N-methylpyrrolidone (NMP) were added. The solvent-resistant pressure tube was evacuated and filled with N 2 repeatedly three times using a double-tube system, and then heated in an oil bath at 110 °C for 2 h in an N 2 atmosphere, and then the temperature was raised to 140 °C and reacted for 2 days. After cooling to room temperature, the product was washed with a large amount of deionized water and tetrahydrofuran until the filtrate was colorless, and then dried under vacuum overnight to obtain the product organic amide polymer material PAAT.

[0042] 2) PAAT was mixed with polyvinylidene fluoride, superconducting carbon black and an appropriate amount of N-methylpyrrolidone (just enough to wet the material powder), and after thorough grinding, it was evenly coated on the surface of the flexible carbon cloth current collector material to obtain the PAAT battery electrode; by mass ratio, PAAT: polyvinylidene fluoride: superconducting carbon black = 7:2:1. After drying, it was weighed, and the mass of the PAAT active material was 1.69 mg.

[0043] Figure 4 It is the charge-discharge curve of the electrode prepared in Example 4 at a current density of 20 A g -1 From the charge-discharge curve, it can be seen that the capacity of PAAT is 38.99 mAh g -1 at a current density of 20 A g -1 , and the rate is 61.81%.

[0044] Example 5

[0045] A method for preparing a PAAT battery electrode for an aqueous ammonium ion battery comprises the following steps:

[0046] 1) Synthesis of PAAT: 0.20 g of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and 0.18 g of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) were placed in a solvent pressure tube, and 0.044 g of zinc acetate and 50 mL of N-methylpyrrolidone (NMP) were added. The solvent pressure tube was repeatedly evacuated three times using a double-row tube and N was passed through. 2 , then in N 2 The solvent pressure tube was heated in an oil bath at 110°C for 2 hours under an atmosphere, and then heated to 140°C for reaction for 2 days. After cooling to room temperature, the product was washed with a large amount of deionized water and tetrahydrofuran until the filtrate was colorless, and vacuum dried overnight to obtain the product organic amide polymer material PAAT.

[0047] 2) PAAT was mixed with polyvinylidene fluoride, superconducting carbon black and an appropriate amount of N-methylpyrrolidone (just enough to wet the material powder), and after being fully ground, it was evenly coated on the surface of the flexible carbon cloth current collector material to obtain a PAAT battery electrode; the mass ratio of PAAT: polyvinylidene fluoride: superconducting carbon black was 7:2:1. After drying and weighing, the mass of PAAT active material was 1.74 mg.

[0048] Figure 5 For PAAT at 10A g -1 Cyclic stability diagram of 1000 charge and discharge cycles at the current density. Figure 5 It can be seen that the capacity retention rate of PAAT is 75.70%.

[0049] Example 6

[0050] A method for preparing a button-type aqueous ammonium ion battery comprises the following steps:

[0051] 1) Synthesis of PAAT: 0.20 g of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and 0.18 g of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) were placed in a solvent pressure tube, and 0.044 g of zinc acetate and 50 mL of N-methylpyrrolidone (NMP) were added. The solvent pressure tube was repeatedly evacuated three times using a double-row tube and N was passed through. 2 , then in N 2 The solvent pressure tube was heated in an oil bath at 110°C for 2 hours under an atmosphere, and then heated to 140°C for reaction for 2 days. After cooling to room temperature, the product was washed with a large amount of deionized water and tetrahydrofuran until the filtrate was colorless, and vacuum dried overnight to obtain the product organic amide polymer material PAAT.

[0052] 2) PAAT is mixed with polyvinylidene fluoride, superconducting carbon black, and an appropriate amount of N-methylpyrrolidone (just enough to wet the material powder), and after thorough grinding, it is evenly coated on the surface of the flexible carbon cloth current collector material to obtain the PAAT battery electrode; by mass ratio, PAAT: polyvinylidene fluoride: superconducting carbon black = 7:2:1. After drying, it is weighed, and the mass of the PAAT active material is 1.66 mg.

[0053] 3) Polyaniline (PANI) is mixed with polyvinylidene fluoride, superconducting carbon black, and an appropriate amount of N-methylpyrrolidone (just enough to wet the material powder), and after thorough grinding, it is evenly coated on the surface of the flexible carbon cloth current collector material to obtain the PANI battery electrode; by mass ratio, PANI: polyvinylidene fluoride: superconducting carbon black = 7:2:1. After drying, it is weighed, and the mass of the PANI active material is 0.99 mg.

[0054] 4) Assembly of the coin cell: Using the PAAT battery electrode as the negative electrode and the PANI battery electrode as the positive electrode, 0.5 M (NH 4 ) 2 SO 4 is used as the electrolyte to assemble the coin cell.

[0055] Figure 6 The figure shows the coin cell powering an LED lamp.

Claims

1. Application of an organic amide polymer material PAAT as an electrode for aqueous ammonium ion batteries.

2. The use according to claim 1, characterized in that: The method is as follows: the organic amide polymer material PAAT is mixed with polyvinylidene fluoride, superconducting carbon black and N-methylpyrrolidone, and after being fully ground, the mixture is evenly coated on the surface of the functionalized flexible carbon cloth current collector material to obtain a battery electrode.

3. The use according to claim 2, characterized in that: In terms of mass ratio, PAAT: polyvinylidene fluoride: superconducting carbon black = 7:2:

1.

4. The use according to claim 2, characterized in that: The amount of N-methylpyrrolidone used is just enough to wet the PAAT, polyvinylidene fluoride and superconducting carbon black powder to form a slurry therewith.

5. The use according to claim 1, characterized in that: The preparation method of the organic amide polymer material PAAT comprises the following steps: placing 3,4,9,10-perylenetetracarboxylic dianhydride and 2,4,6-tris(4-aminophenyl)-1,3,5-triazine into a solvent pressure tube, and adding a catalyst zinc acetate and a solvent N-methylpyrrolidone; heating the solvent pressure tube in an oil bath at 110° C. for 2 h under a N2 atmosphere, and then heating the tube to 140° C. for reaction for 2 days; cooling the tube to room temperature, washing the product with a large amount of deionized water and tetrahydrofuran until the filtrate is colorless, and vacuum drying the product overnight to obtain the product organic amide polymer material PAAT.

6. The use according to claim 5, characterized in that: In terms of molar ratio, 3,4,9,10-perylenetetracarboxylic dianhydride: 2,4,6-tris(4-aminophenyl)-1,3,5-triazine: zinc acetate = 5:5:

2.

7. The use according to claim 5, characterized in that: The amount of N-methylpyrrolidone used is enough to immerse 3,4,9,10-perylenetetracarboxylic dianhydride, 2,4,6-tris(4-aminophenyl)-1,3,5-triazine and zinc acetate powder.

8. The use according to claim 5, characterized in that: The N2 atmosphere is formed by repeatedly evacuating the atmosphere three times using a double row of tubes and passing N2 therethrough.

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