Preparation method of composite organic material for aqueous ammonium ion battery

Abstract

The invention belongs to the technical field of energy storage materials, and particularly relates to a preparation method of a composite organic material for an aqueous ammonium ion battery. According to the invention, 3, 4, 9, 10-perylenetetracarboxylic dianhydride and 2, 6-diamino-anthraquinone are subjected to an amide polycondensation reaction to prepare the chain-like organic polymer material PTDA. The anhydride monomer and the amine monomer are combined to form the chain-shaped organic polymer material, so that the structural stability of the material is improved, and the improvement of the electrochemical performance of the battery is facilitated.

Description

Technical Field

[0001] The present invention belongs to the technical field of energy storage materials, and particularly relates to a preparation method of a composite organic material for an aqueous ammonium ion battery. Background Art

[0002] Existing lithium-ion batteries have disadvantages such as a shortage of lithium metal and the toxicity, inflammability, and explosiveness of organic electrolytes. The aqueous ammonium ion battery uses an aqueous solution as the electrolyte, has the advantages of environmental friendliness, safety, and low cost, and has good development prospects. However, at the same time, the limited electrochemical performance of the energy storage materials of the aqueous ammonium ion battery restricts its commercial development and has become one of the current hot research topics. As the center of the battery redox reaction, the electrode material is the medium responsible for both ion and electron transfer and separation, and largely determines the performance of the entire battery. Therefore, the exploration of electrode materials for aqueous ammonium ion batteries is crucial. Organic materials often have a large number of nitrogen and oxygen functional groups, and can form hydrogen bonds with NH 4 + to achieve NH 4 + storage, and are a promising class of ammonium storage materials. Organic small molecules have problems such as easy dissolution, unstable structure, and are prone to aggregation and stacking, which greatly affects the performance of the electrode material. 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 2,6-diaminoanthraquinone atoms to prepare a chain-like organic polymer material 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 a preparation method of a composite organic material for an aqueous ammonium ion battery.

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

[0006] A preparation method of a composite organic material for an aqueous ammonium ion battery, comprising the following steps: putting 3,4,9,10-perylene tetracarboxylic dianhydride and 2,6-diaminoanthraquinone into a solvent pressure-resistant tube, adding a catalyst zinc acetate and a solvent N-methylpyrrolidone, and under N 2 atmosphere, heating the solvent pressure-resistant tube in an oil bath at 110°C for 2 h, then raising the temperature to 140°C and reacting for 2 days. After cooling to room temperature, washing the product and drying it under vacuum overnight to obtain the product composite organic material PTDA.

[0007] Further, in the above preparation method, by molar ratio, 3,4,9,10-perylene tetracarboxylic dianhydride:2,6-diaminoanthraquinone:zinc acetate = 5:5:2.

[0008] Further, in the above preparation method, the amount of N-methylpyrrolidone used is such that it submerges 3,4,9,10-perylenetetracarboxylic dianhydride, 2,6-diaminoanthraquinone, and zinc acetate powder.

[0009] Further, in the above preparation method, the N 2 The atmosphere is achieved by repeatedly evacuating and introducing N using a double-tube for three times. 2 .

[0010] Further, in the above preparation method, the washing method should be: washing the product with a large amount of deionized water and tetrahydrofuran respectively until the filtrate is colorless.

[0011] Application of PTDA prepared by the preparation method described in any one of the above as an electrode material for an aqueous ammonium ion battery.

[0012] Further, in the above application, the method is as follows: Mix PTDA with polyvinylidene fluoride, superconducting carbon black, and N-methylpyrrolidone, and after thoroughly grinding, evenly coat it on the surface of a functionalized flexible carbon cloth current collector material to obtain a battery electrode.

[0013] Furthermore, in the above application, by mass ratio, PTDA: polyvinylidene fluoride: superconducting carbon black = 7:2:1.

[0014] Furthermore, in the above application, the amount of N-methylpyrrolidone used is just enough to wet PTDA, polyvinylidene fluoride, and superconducting carbon black powders and form a slurry with them.

[0015] The beneficial effects of the present invention are:

[0016] 1. The present invention utilizes the nucleophilic reaction between the carbonyl carbon atom in 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and the nitrogen atom in 2,6-diaminoanthraquinone to prepare a chain-like organic polymer material PTDA with multiple active sites. Organic small molecules have problems such as easy dissolution, unstable structure, and are prone to aggregation and stacking, which greatly affects the performance of electrode materials. The present invention combines an anhydride monomer with an amine monomer to form a chain-like organic polymer material, increasing the structural stability of the material and being beneficial to the improvement of the battery cycle stability performance.

[0017] 2. The PTDA material synthesized by the present invention is a large molecule in the form of a long chain, and this active substance is more stable, which is beneficial to the improvement of cycle stability. Description of the Drawings

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

[0019] Figure 2It is the cyclic voltammogram of the PTDA electrode prepared in Example 2 at a scan rate of 20 mV / s.

[0020] Figure 3 It is the charge-discharge curve of the PTDA electrode prepared in Example 3 at a current density of 1 Ag -1

[0021] Figure 4 It is the charge-discharge curve of the PTDA electrode prepared in Example 4 at a current density of 10 Ag -1

[0022] Figure 5 It is the charge-discharge curve of the PTDA electrode prepared in Example 5 at a current density of 10 Ag -1 and the cyclic curve of 1000 charge-discharge cycles.

[0023] Figure 6 It is the physical diagram of the button ammonium ion battery prepared in Example 6 powering a small fan.

[0024] Figure 7 It is the PTDA synthesis reaction formula. Detailed implementation mode

[0025] Example 1

[0026] A preparation method of a composite organic material for an aqueous ammonium ion battery, comprising the following steps:

[0027] Synthesis of PTDA (as Figure 7 ): Put 0.20 g of 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) and 0.12 g of 2,6-diaminoanthraquinone into a solvent pressure-resistant tube, add 0.044 g of zinc acetate and 50 mL of N-methylpyrrolidone (NMP), and use a double-tube to repeatedly evacuate and fill the solvent pressure-resistant tube with N 2 , and then heat the solvent pressure-resistant tube in an oil bath at 110 °C for 2 h under an N 2 atmosphere, 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 PTDA.

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

[0029] Example 2

[0030] A preparation method of a PTDA electrode for an aqueous ammonium ion battery, comprising the following steps:

[0031] ​​1) Synthesis of PTDA: 0.20 g of 3,4,9,10 - perylene tetracarboxylic dianhydride (PTCDA) and 0.12 g of 2,6 - diaminoanthraquinone were placed into 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 three times repeatedly using a double - row tube, and then 2 under a N

[0032] atmosphere, the solvent - resistant pressure tube was heated in an oil bath at 110 °C for 2 h, 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 PTDA.

[0033] Figure 2 Figure -1 is the cyclic voltammogram of the PTDA electrode prepared in Example 2 at a scan rate of 20 mV s Figure 2 . It can be determined that the voltage range of PTDA is - 1.2 to 0 V.

[0034] Example 3

[0035] A preparation method of a PTDA electrode for an aqueous ammonium - ion battery, comprising the following steps:

[0036] 1) Synthesis of PTDA: 0.20 g of 3,4,9,10 - perylene tetracarboxylic dianhydride (PTCDA) and 0.12 g of 2,6 - diaminoanthraquinone were placed into 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 three times repeatedly using a double - row tube, and then 2 under a N

[0037] atmosphere, the solvent - resistant pressure tube was heated in an oil bath at 110 °C for 2 h, 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 PTDA.

[0038] Figure 3 The PTDA electrode prepared in Example 3 was -1 The charge and discharge curves under current density. It can be seen from the charge and discharge curves that PTDA -1 The capacity can reach 83.68 mAh g at the current density -1 .

[0039] Example 4

[0040] A method for preparing a PTDA electrode for an aqueous ammonium ion battery comprises the following steps:

[0041] 1) Synthesis of PTDA: 0.20 g of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and 0.12 g of 2,6-diaminoanthraquinone 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 with a double-row tube and N was passed through. 2 , then in N 2 The solvent was heated in a pressure tube at 110°C in an oil bath for 2 h 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 PTDA.

[0042] 2) PTDA was mixed with polyvinylidene fluoride, superconducting carbon black and an appropriate amount of N-methylpyrrolidone (just enough to wet the material powder) to form a slurry, which was fully ground and evenly coated on the surface of the flexible carbon cloth current collector material to obtain a PTDA electrode; the mass ratio of PTDA: polyvinylidene fluoride: superconducting carbon black was 7:2:1. After drying and weighing, the mass of PTDA active material was 1.73 mg.

[0043] Figure 4 The PTDA electrode prepared in Example 4 was -1 The charge and discharge curves under current density. It can be seen from the charge and discharge curves that PTDA -1 The capacity at the current density is 49.46 mAh g -1 , the magnification is 59.11%.

[0044] Example 5

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

[0046] 1) Synthesis of PTDA: Put 0.20 g of 3,4,9,10 - perylene tetracarboxylic dianhydride (PTCDA) and 0.12 g of 2,6 - diaminoanthraquinone into a solvent - resistant pressure tube, add 0.044 g of zinc acetate and 50 mL of N - methylpyrrolidone (NMP). Use a double - row tube to evacuate and fill the solvent - resistant pressure tube with N 2 , and then under N 2 atmosphere, heat the solvent - resistant pressure 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 under vacuum overnight to obtain the product PTDA.

[0047] 2) Mix PTDA with polyvinylidene fluoride, superconducting carbon black and an appropriate amount of N - methylpyrrolidone (just enough to wet the material powder) to form a slurry. After thorough grinding, evenly coat it on the surface of a flexible carbon cloth current collector material to obtain a PTDA electrode; by mass ratio, PTDA: polyvinylidene fluoride: superconducting carbon black = 7:2:1. After drying, weigh it, and the mass of the PTDA active material is 1.74 mg.

[0048] Figure 5 This is the cyclic stability diagram of the PTDA electrode at a current density of 10 Ag -1 for 1000 charge - discharge cycles. As can be seen from Figure 5 , the capacity retention rate of PTDA is 67.37%.

[0049] Example 6

[0050] A preparation method of a button - type aqueous ammonium - ion battery, comprising the following steps:

[0051] 1) Synthesis of PTDA: Put 0.20 g of 3,4,9,10 - perylene tetracarboxylic dianhydride (PTCDA) and 0.12 g of 2,6 - diaminoanthraquinone into a solvent - resistant pressure tube, add 0.044 g of zinc acetate and 50 mL of N - methylpyrrolidone (NMP). Use a double - row tube to evacuate and fill the solvent - resistant pressure tube with N 2 , and then under N 2 atmosphere, heat the solvent - resistant pressure 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 under vacuum overnight to obtain the product PTDA.

[0052] 2) Mix PTDA with polyvinylidene fluoride, superconducting carbon black and an appropriate amount of N - methylpyrrolidone (just enough to wet the material powder) to form a slurry. After thorough grinding, evenly coat it on the surface of a flexible carbon cloth current collector material to obtain a PTDA electrode; by mass ratio, PTDA: polyvinylidene fluoride: superconducting carbon black = 7:2:1. After drying, weigh it, and the mass of the PTDA active material is 1.81 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 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 0.78 mg.

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

[0055] Figure 6 The actual picture of the coin cell powering a small fan.

Claims

1. A method for preparing a composite organic material for an aqueous ammonium ion battery, characterized in that: The method comprises the following steps: placing 3,4,9,10-perylenetetracarboxylic dianhydride and 2,6-diaminoanthraquinone into a solvent pressure tube, adding a catalyst zinc acetate and a solvent N-methylpyrrolidone, heating the solvent pressure tube in an oil bath at 110° C. for 2 hours under a N2 atmosphere, then heating the tube to 140° C. for reaction for 2 days, cooling the tube to room temperature, washing the product, and vacuum drying the product overnight to obtain a product composite organic material PTDA.

2. The preparation method according to claim 1, characterized in that: In terms of molar ratio, 3,4,9,10-perylenetetracarboxylic dianhydride:2,6-diaminoanthraquinone:zinc acetate=5:5:

2.

3. The preparation method according to claim 1, characterized in that: The amount of N-methylpyrrolidone used is enough to immerse the 3,4,9,10-perylenetetracarboxylic dianhydride, 2,6-diaminoanthraquinone and zinc acetate powder.

4. The preparation method according to claim 1, 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.

5. The preparation method according to claim 1, characterized in that: The washing method should be: washing the product with a large amount of deionized water and tetrahydrofuran respectively until the filtrate is colorless.

6. Use of the PTDA prepared by the preparation method according to any one of claims 1 to 5 as an electrode material for aqueous ammonium ion batteries.

7. The use according to claim 6, characterized in that: The method is as follows: PTDA 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 a functionalized flexible carbon cloth current collector material to obtain a battery electrode.

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

1.

9. The use according to claim 7, characterized in that: The amount of N-methylpyrrolidone used is just enough to wet the PTDA, polyvinylidene fluoride and superconducting carbon black powder to form a slurry therewith.

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