Preparation method and application of organic polymer material with photoelectric response

Abstract

The invention belongs to the technical field of energy storage materials, and particularly provides a preparation method and application of an organic polymer material with photoelectric response. The organic polymer material is prepared by carrying out condensation polymerization on 2, 5-dihydroxy-1, 4-benzoquinone and 2, 3, 5, 6-tetraamino-1, 4-benzoquinone, and the organic polymer material is prepared by carrying out condensation polymerization on the 2, 5-dihydroxy-1, 4-benzoquinone and the 2, 3, 5, 6-tetraamino-1 The organic polymer material is a linear polymer with stable physical and chemical properties, and has rich carbon-oxygen double bonds, carbon-nitrogen double bonds and carbon-carbon double bonds with electrochemical reaction activity and a stable trapezoidal polymer skeleton, so that the organic polymer material has good capacity in the ammonium ion battery. In addition, the organic polymer material shows more excellent electrochemical performance under illumination, especially extremely high cycling stability.

Description

Technical Field

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

[0002] In recent years, with the exhaustion of fossil energy and the aggravation of environmental pollution, the research and development of new energy storage materials have received increasing attention. Existing lithium-ion batteries have disadvantages such as shortage of lithium metal and toxicity, flammability and explosiveness of organic electrolytes. Aqueous ammonium ion batteries use aqueous solutions as electrolytes, which have the advantages of environmental friendliness, safety, low cost, etc., and have good development prospects. However, at the same time, the limited electrochemical performance of the energy storage materials of aqueous ammonium ion batteries restricts their commercial development and has become one of the current hot research topics. As the center of the battery redox reaction, the electrode material is a medium that is 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, which can form hydrogen bonds with NH4 + to achieve NH4 + 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 have a great impact on the performance of the electrode material. A series of methods have been used to solve the cyclic stability problem of organic small molecule materials, such as using small molecule salts with lower solubility, using solid electrolytes to inhibit the dissolution of small molecules, or introducing redox-active functional groups into the stable skeleton of polymers to improve the cycle life. Among them, using organic polymers containing redox-active functional groups as electrode materials can significantly improve the cyclic stability of ammonium ion batteries, but due to the introduction of redox-inactive functional groups in the polymer skeleton, the specific capacity of the battery is relatively low. And light can excite photoelectrons in semiconductor materials to form photocurrent, further improving the electrochemical performance of the electrode material. Summary of the Invention

[0003] To effectively solve the above problems, the present invention provides a preparation method and application of an organic polymer material with photoelectric response.

[0004] The technical solution adopted by the present invention is as follows:

[0005] A preparation method of an organic polymer material with optoelectronic response, comprising the following steps: adding 2,5-dihydroxy-1,4-benzoquinone and 2,3,5,6-tetraamino-1,4-benzoquinone into a three-necked round-bottom flask, slowly adding N-methylpyrrolidone solvent and five drops of phosphoric acid aqueous solution at room temperature under the protection of argon, stirring and dissolving to mix evenly at the same time, heating the reaction by an oil bath, after the reaction is completed, allowing the reaction system to stand and cool to room temperature, collecting the solid crude product by suction filtration, performing the operations of washing and suction filtration repeatedly with methanol, water, and ethanol, and further performing Soxhlet extraction and washing with methanol, water, ethanol, and acetone until the filtrate is colorless, drying the solid in vacuo to obtain a purified black solid powder product, namely a ladder polymer.

[0006] Further, in the above preparation method, the molar ratio of 2,5-dihydroxy-1,4-benzoquinone to 2,3,5,6-tetraamino-1,4-benzoquinone is 1:1.

[0007] Furthermore, in the above preparation method, the dosages of both 2,5-dihydroxy-1,4-benzoquinone and 2,3,5,6-tetraamino-1,4-benzoquinone are 2 mmol.

[0008] Further, in the above preparation method, the mass percentage concentration of phosphoric acid in the phosphoric acid aqueous solution is 85%.

[0009] Further, in the above preparation method, the conditions for the heating reaction are to maintain the reaction at 100 °C for 12 h.

[0010] Further, in the above preparation method, the conditions for the vacuum drying are to dry in vacuo at 80 °C overnight.

[0011] Application of the organic polymer material with optoelectronic response 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: mixing the organic polymer material with optoelectronic response with polyvinylidene fluoride, superconducting carbon black, and N-methylpyrrolidone, thoroughly grinding and then uniformly coating 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, the organic polymer material with optoelectronic response: polyvinylidene fluoride: superconducting carbon black = 7:2:1, and N-methylpyrrolidone just infiltrates the above three material powders to form a slurry with them.

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

[0015] 1. The polymer synthesized in the present invention is a macromolecule in the form of a long chain, and this active substance is more stable, which is beneficial to improving the cycle stability.

[0016] 2. The polymer synthesized by the present invention has a light response, further improving the electrochemical performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is an infrared spectrogram of the organic polymer material with optoelectronic response synthesized in Example 1.

[0018] Figure 2 It is a cyclic voltammogram of the ladder polymer battery electrode prepared in Example 2 under sunlight irradiation at a scan rate of 10 mV / s.

[0019] Figure 3 It is a comparison chart of charge-discharge curves of the ladder polymer battery electrode prepared in Example 3 at a current density of 1 Ag -1 under the conditions of with / without sunlight irradiation.

[0020] Figure 4 It is a comparison chart of charge-discharge curves of the ladder polymer battery electrode prepared in Example 4 at a current density of 10 Ag-1 under the conditions of with / without sunlight irradiation.

[0021] Figure 5 It is a cyclic voltammogram of the ladder polymer battery electrode prepared in Example 5 at a current density of 10 Ag -1 with 5500 charge-discharge cycles.

[0022] Figure 6 It is a physical diagram of a button battery powering a small fan.

[0023] Figure 7 It is the chemical structural formula of the organic polymer material with optoelectronic response. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0024] Example 1

[0025] A preparation method of an organic polymer material with optoelectronic response, comprising the following steps:

[0026] Synthesis of Ladder Polymer: 280 mg (2 mmol) of 2,5-dihydroxy-1,4-benzoquinone and 336 mg (2 mmol) of 2,3,5,6-tetraamino-1,4-benzoquinone were added together into a 50 mL three-necked round-bottom flask. Under the protection of argon, 20 mL of N-methylpyrrolidone solvent and five drops of 85 wt% phosphoric acid aqueous solution were slowly added at room temperature. At the same time, it was stirred and dissolved to mix evenly. It was heated to 100 °C by an oil bath and reacted at 100 °C for 12 h. After the reaction was completed, the reaction system was allowed to stand and cool to room temperature. The solid crude product was collected by suction filtration. The operations of washing and suction filtration were repeatedly carried out using solvents such as methanol, water, and ethanol. Further, Soxhlet extraction and washing were carried out with methanol, water, ethanol, and acetone until the filtrate was colorless. The solid was dried in vacuo at 80 °C overnight to obtain a purified black solid powder product, namely the ladder polymer.

[0027] Figure 1 It is the infrared spectrum of the ladder polymer synthesized in Example 1. In the infrared peaks of this ladder polymer, the infrared characteristic peak of the C=O bond at 1626 cm -1 and the infrared characteristic peak of the C=N bond at 1545 cm -1 can be clearly seen.

[0028] Example 2

[0029] A preparation method of an organic polymer material with optoelectronic response, comprising the following steps:

[0030] 1) Synthesis of Ladder Polymer: 280 mg (2 mmol) of 2,5-dihydroxy-1,4-benzoquinone and 336 mg (2 mmol) of 2,3,5,6-tetraamino-1,4-benzoquinone were added together into a 50 mL three-necked round-bottom flask. Under the protection of argon, 20 mL of N-methylpyrrolidone solvent and five drops of 85 wt% phosphoric acid aqueous solution were slowly added at room temperature. At the same time, it was stirred and dissolved to mix evenly. It was heated to 100 °C by an oil bath and reacted at 100 °C for 12 h. After the reaction was completed, the reaction system was allowed to stand and cool to room temperature. The solid crude product was collected by suction filtration. The operations of washing and suction filtration were repeatedly carried out using solvents such as methanol, water, and ethanol. Further, Soxhlet extraction and washing were carried out with methanol, water, ethanol, and acetone until the filtrate was colorless. The solid was dried in vacuo at 80 °C overnight to obtain a purified black solid powder product, namely the ladder polymer.

[0031] 2) The ladder polymer is mixed with polyvinylidene fluoride, superconducting carbon black and N-methylpyrrolidone. The N-methylpyrrolidone just soaks the powders of the above three materials. After sufficient grinding, it is evenly coated on the surface of the flexible carbon cloth current collector material to obtain a ladder polymer battery electrode; according to the mass ratio, the ladder polymer: polyvinylidene fluoride: superconducting carbon black = 7:2:1. After drying and weighing, the mass of the ladder polymer active material is 1.55mg.

[0032] Figure 2 The battery electrode prepared in Example 2 is 10 mV s -1 Cyclic voltammetry curve at the scan rate. Figure 2 The voltage range of the ladder polymer can be determined to be -0.8 to 0.7V.

[0033] Example 3

[0034] A method for preparing an organic polymer material having a photoelectric response comprises the following steps:

[0035] 1) Synthesis of ladder polymer: 280 mg (2 mmol) of 2,5-dihydroxy-1,4-benzoquinone and 336 mg (2 mmol) of 2,3,5,6-tetraamino-1,4-benzoquinone were added to a 50 mL three-necked round-bottom flask. Under the protection of argon, 20 mL of N-methylpyrrolidone solvent and five drops of 85 wt% phosphoric acid aqueous solution were slowly added at room temperature, and the mixture was stirred and dissolved uniformly. The mixture was heated to 100° C. by oil bath heating and maintained at 100° C. for 12 h. After the reaction was completed, the reaction system was allowed to stand and cool to room temperature. The crude solid product was collected by suction filtration, and the washing and suction filtration were repeated using methanol, water, ethanol and other solvents. The filtrate was further washed by Soxhlet extraction with methanol, water, ethanol and acetone until the filtrate was colorless. The solid was vacuum dried at 80° C. overnight to obtain a purified black solid powder product, i.e., a ladder polymer.

[0036] 2) The ladder polymer is mixed with polyvinylidene fluoride, superconducting carbon black and N-methylpyrrolidone. The N-methylpyrrolidone just soaks the powders of the above three materials. After sufficient grinding, it is evenly coated on the surface of the flexible carbon cloth current collector material to obtain a ladder polymer battery electrode; according to the mass ratio, the ladder polymer: polyvinylidene fluoride: superconducting carbon black = 7:2:1. After drying and weighing, the mass of the active materials of the two ladder polymer electrodes is 1.63mg.

[0037] Figure 3 The charge and discharge curves of the battery electrode prepared in Example 3 under different light conditions are shown in FIG. 1 . As can be seen from the charge and discharge curves, under light conditions, the ladder polymer -1 The capacity can reach 187.19 mAh g at the current density -1 Without light, the capacity of the ladder polymer is 130.59 mAh g-1 。

[0038] Example 4

[0039] A preparation method of an organic polymer material with photoelectric response, comprising the following steps:

[0040] 1) Synthesis of ladder polymer: Add 280 mg (2 mmol) of 2,5-dihydroxy-1,4-benzoquinone and 336 mg (2 mmol) of 2,3,5,6-tetraamino-1,4-benzoquinone into a 50 mL three-necked round-bottom flask. Under the protection of argon, slowly add 20 mL of N-methylpyrrolidone solvent and five drops of 85 wt% phosphoric acid aqueous solution at room temperature, and stir and dissolve to mix evenly. Heat up to 100 °C by oil bath heating and keep reacting at 100 °C for 12 h. After the reaction is completed, let the reaction system stand and cool to room temperature. Collect the solid crude product by suction filtration, and repeatedly wash and filter with solvents such as methanol, water, and ethanol. Further perform Soxhlet extraction and washing with methanol, water, ethanol, and acetone until the filtrate is colorless. Dry the solid overnight in a vacuum at 80 °C to obtain a purified black solid powder product, namely the ladder polymer.

[0041] 2) Mix the ladder polymer with polyvinylidene fluoride, superconducting carbon black, and N-methylpyrrolidone. The N-methylpyrrolidone just wets the above three material powders. After sufficient grinding, evenly coat it on the surface of the flexible carbon cloth current collector material to obtain a ladder polymer battery electrode; by mass ratio, ladder polymer: polyvinylidene fluoride: superconducting carbon black = 7:2:1. Weigh it after drying. The mass of the active material of both ladder polymer electrodes is 1.63 mg.

[0042] Figure 4 are the charge-discharge curves of the electrode prepared in Example 4 under different light conditions. It can be seen from the charge-discharge curves that under light conditions, the capacity of the ladder polymer can reach 44.30 mAh g -1 at a current density of 10 Ag -1 while under the condition of no light, the capacity of the ladder polymer is 35.02 mAh g -1 。

[0043] Example 5

[0044] A preparation method of an organic polymer material with photoelectric response, comprising the following steps:

[0045] 1) Synthesis of ladder polymer: 280 mg (2 mmol) of 2,5-dihydroxy-1,4-benzoquinone and 336 mg (2 mmol) of 2,3,5,6-tetraamino-1,4-benzoquinone were added to a 50 mL three-necked round-bottom flask. Under the protection of argon, 20 mL of N-methylpyrrolidone solvent and five drops of 85 wt% phosphoric acid aqueous solution were slowly added at room temperature, and the mixture was stirred and dissolved uniformly. The mixture was heated to 100° C. by oil bath heating and maintained at 100° C. for 12 h. After the reaction was completed, the reaction system was allowed to stand and cool to room temperature. The crude solid product was collected by suction filtration, and the washing and suction filtration were repeated using methanol, water, ethanol and other solvents. The filtrate was further washed by Soxhlet extraction with methanol, water, ethanol and acetone until the filtrate was colorless. The solid was vacuum dried at 80° C. overnight to obtain a purified black solid powder product, i.e., a ladder polymer.

[0046] 2) The ladder polymer is mixed with polyvinylidene fluoride, superconducting carbon black and N-methylpyrrolidone. The N-methylpyrrolidone just soaks the powders of the above three materials. After sufficient grinding, it is evenly coated on the surface of the flexible carbon cloth current collector material to obtain a ladder polymer battery electrode; according to the mass ratio, the ladder polymer: polyvinylidene fluoride: superconducting carbon black = 7:2:1. After drying and weighing, the mass of the active materials of the two ladder polymer electrodes is 1.69 mg.

[0047] Figure 5 For ladder polymers under light conditions, 10Ag -1 Cyclic stability diagram of 5500 charge and discharge cycles at the current density. Figure 5 It can be seen that the capacity retention rate of the ladder polymer is approximately 100%.

[0048] Example 6

[0049] A method for preparing an organic polymer material having a photoelectric response comprises the following steps:

[0050] 1) Synthesis of ladder polymer: 280 mg (2 mmol) of 2,5-dihydroxy-1,4-benzoquinone and 336 mg (2 mmol) of 2,3,5,6-tetraamino-1,4-benzoquinone were added to a 50 mL three-necked round-bottom flask. Under the protection of argon, 20 mL of N-methylpyrrolidone solvent and five drops of 85 wt% phosphoric acid aqueous solution were slowly added at room temperature, and the mixture was stirred and dissolved uniformly. The mixture was heated to 100° C. by oil bath heating and maintained at 100° C. for 12 h. After the reaction was completed, the reaction system was allowed to stand and cool to room temperature. The crude solid product was collected by suction filtration, and the washing and suction filtration were repeated using methanol, water, ethanol and other solvents. The filtrate was further washed by Soxhlet extraction with methanol, water, ethanol and acetone until the filtrate was colorless. The solid was vacuum dried at 80° C. overnight to obtain a purified black solid powder product, i.e., a ladder polymer.

[0051] 2) The ladder polymer is mixed with polyvinylidene fluoride, superconducting carbon black, and N-methylpyrrolidone. N-methylpyrrolidone just wets the above three material powders. After thorough grinding, it is evenly coated on the surface of the flexible carbon cloth current collector material to obtain the ladder polymer battery electrode. By mass ratio, ladder polymer: polyvinylidene fluoride: superconducting carbon black = 7:2:1. After drying and weighing, the mass of the active substance of the ladder polymer electrode is 1.83 mg.

[0052] 3) Electrodeposit MnO on the carbon cloth at a constant voltage of 1.8 V in 0.2 M Mn(Ac)2 solution for 3 min to obtain electrodeposited MnO. After drying and weighing, the weight is 1.30 mg.

[0053] 4) Assemble a button cell with the electrodeposited MnO as the positive electrode, the ladder polymer as the negative electrode, and 0.5 M (NH4)2SO4 as the electrolyte.

[0055] Figure 6 The figure of the button cell powering a small fan is shown.

Claims

1. A preparation method of an organic polymer material with optoelectronic response, characterized in that, It includes the following steps: Add 2,5-dihydroxy-1,4-benzoquinone and 2,3,5,6-tetraamino-1,4-benzoquinone into a three-necked round-bottom flask. Under the protection of argon, slowly add N-methylpyrrolidone solvent and five drops of phosphoric acid aqueous solution at room temperature, and stir and dissolve them evenly. Heat the reaction by an oil bath. After the reaction is completed, let the reaction system stand and cool to room temperature. Collect the solid crude product by suction filtration, and repeatedly wash and filter it with methanol, water, and ethanol. Then further perform Soxhlet extraction and washing with methanol, water, ethanol, and acetone until the filtrate is colorless. Vacuum dry the solid to obtain a purified black solid powder product, that is, the ladder polymer.

2. The preparation method according to claim 1, characterized in that, The molar ratio of 2,5-dihydroxy-1,4-benzoquinone to 2,3,5,6-tetraamino-1,4-benzoquinone is 1:

1.

3. The preparation method according to claim 2, characterized in that, The dosage of both 2,5-dihydroxy-1,4-benzoquinone and 2,3,5,6-tetraamino-1,4-benzoquinone is 2 mmol.

4. The preparation method according to claim 1, characterized in that, The mass percentage concentration of phosphoric acid in the phosphoric acid aqueous solution is 85%.

5. The preparation method according to claim 1, characterized in that, The conditions for the heating reaction are to maintain the reaction at 100 °C for 12 h.

6. The preparation method according to claim 1, wherein The conditions for the vacuum drying are to vacuum dry overnight at 80 °C.

7. Application of the organic polymer material with optoelectronic response prepared by the preparation method described in any one of claims 1-6 as an electrode material for an aqueous ammonium ion battery.

8. The application according to claim 7, characterized in that, The method is as follows: Mix the organic polymer material with optoelectronic response, polyvinylidene fluoride, superconducting carbon black, and N-methylpyrrolidone, and evenly coat the mixture on the surface of the functionalized flexible carbon cloth current collector material after sufficient grinding to obtain a battery electrode.

9. The application according to claim 8, characterized in that, By mass ratio, the organic polymer material with optoelectronic response: polyvinylidene fluoride: superconducting carbon black = 7:2:1, and N-methylpyrrolidone just wets the above three material powders to form a slurry with them.

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