CN115331975B - Integrated anti-freezing supercapacitor and preparation method thereof - Google Patents

Abstract

An integral anti-freezing supercapacitor and a preparation method thereof comprise the following steps: (1) Adding a monomer, nano particles, electrolyte salt, a cross-linking agent, an initiator and small molecular alcohol into deionized water, stirring and blending, and polymerizing after ultrasonic treatment to obtain an antifreeze gel electrolyte; (2) Immersing the antifreeze gel electrolyte in a conductive polymer monomer solution, and then adding persulfate to polymerize the conductive polymer electrode on the electrolyte surface in situ; (3) Cutting the periphery of the conductive polymer composite gel electrolyte to obtain the integrated anti-freezing supercapacitor. The antifreeze gel electrolyte is prepared by adopting a compounding method, and the preparation process is simple and easy to implement; an in-situ polymerization mode is adopted to obtain the integrated flexible supercapacitor, so that the use of toxic and harmful conductive adhesive is avoided; the integrated flexible supercapacitor obtained by the invention has good deformation resistance and excellent low temperature resistance.

Description

Integrated antifreeze supercapacitor and preparation method thereof

Technical field

The invention relates to the field of energy storage materials and devices, and in particular to an integrated anti-freeze supercapacitor and a preparation method thereof.

Background technique

With the rapid development of wearable electronics technology, flexible supercapacitors have received widespread attention in industry and academia due to their advantages such as high power density, long cycle life, and fast charge and discharge rates. In order to meet the needs of wearable electronic products in practical applications, supercapacitors must have certain deformation resistance and low temperature resistance. The electrochemical performance of flexible supercapacitors is generally determined by the electrode, electrolyte and device configuration. Flexible self-supporting electrodes, such as carbon nanomaterials (such as carbon nanotubes, graphene, etc.) and conductive polymers (such as polyaniline, polypyrrole, etc.), have been widely studied for determining the energy density of flexible supercapacitors. Flexible electrolytes are generally hydrogel electrolytes. Since water freezes at low temperatures, the hydrogel electrolyte will freeze, thus reducing the ion migration rate in the electrolyte, thereby reducing the electrochemical performance of the supercapacitor. In addition, the configuration of the supercapacitor determines the anti-deformation characteristics of the supercapacitor during actual operation to a certain extent. For example, during stretching, twisting, bending, etc. of a supercapacitor, if the interface contact between the electrodes and electrolytes is not good, the adjacent layers will slip or even fall off, thereby reducing the performance of the device. At present, the use of in-situ polymerization of electrodes on the electrolyte promotes the contact between the electrode and the electrolyte to a certain extent (113571343A) and improves the mechanical properties of the supercapacitor, but it still fails at low temperatures. Therefore, there is an urgent need to develop a flexible supercapacitor with certain deformation resistance and low temperature resistance by adjusting the electrode, electrolyte properties and device configuration.

Contents of the invention

Technical problem solved: In order to improve the problems of insufficient deformation resistance and low temperature resistance of flexible supercapacitors, the present invention provides a simple and easy integrated anti-freeze supercapacitor and its preparation method.

Technical solution: Preparation method of integrated antifreeze supercapacitor, including the following steps: (1) Combine 1~10g monomer, 1~10g nanoparticles, 1~10g electrolyte salt, 1~100mg cross-linking agent, 1~100mg initiator Add agent and 2~20g small molecular alcohol to 2~20g deionized water, stir and blend at 100~1000rmp, ultrasonic at 0~5℃ for 1~30 minutes, ultrasonic power is 100~500W, polymerize at 50~120℃ for 1~10 Obtain the antifreeze gel electrolyte in 2 hours; (2) Soak the antifreeze gel electrolyte in the conductive polymer monomer solution for 10 to 150 minutes, add persulfate and react for 10 to 200 minutes. The conductive polymer monomer reacts with the conductive polymer monomer. The sulfate mass ratio is 1~10:1~30; (3) Cut around the conductive polymer composite gel electrolyte to obtain an integrated anti-freeze supercapacitor.

Preferably, the monomer in the above step (1) is polyethylene glycol, acrylamide or acrylic acid.

Preferably, the nanoparticles in the above step (1) are nanosilica or nanohydroxyapatite.

Preferably, the electrolyte salt in the above step (1) is lithium chloride, potassium chloride or zinc chloride.

Preferably, the cross-linking agent in the above step (1) is N,N'-methylene bisacrylamide or polyethylene glycol bisacrylamide.

Preferably, the initiator in the above step (1) is ammonium persulfate or potassium persulfate.

Preferably, the small molecular alcohol in the above step (1) is ethylene glycol or glycerin.

Preferably, the conductive polymer monomer in the above step (2) is aniline or pyrrole.

Preferably, the persulfate in the above step (2) is ammonium persulfate or potassium persulfate.

An integrated antifreeze supercapacitor prepared by the above preparation method.

The purpose of the present invention is to provide a new idea. First, a flexible antifreeze hydrogel electrolyte is prepared, and then a conductive polymer electrode is polymerized in situ on the gel matrix to obtain an integrated antifreeze supercapacitor with improved flexibility. The problems of insufficient resistance to deformation and low temperature resistance of supercapacitors have expanded the application scope of flexible supercapacitors.

Beneficial effects: 1. The low-temperature resistant hydrogel electrolyte is prepared by a compounding method, and the preparation process is simple and easy; 2. An integrated flexible supercapacitor is obtained by in-situ polymerization, avoiding the use of toxic and harmful conductive glue; 3. Obtained The integrated flexible supercapacitor has good deformation resistance and excellent low-temperature resistance. For example, the integrated anti-freeze supercapacitor prepared in Example 1 can power an electronic watch under low-temperature stretching, which solves the problem of flexible supercapacitors’ resistance to resistance. The problems of insufficient performance in deformation and low temperature resistance have expanded the application range of flexible supercapacitors in wearable electronics.

Description of the drawings

Figure 1 is a schematic diagram of the preparation of an integrated antifreeze supercapacitor. The device consists of a low-temperature-resistant hydrogel electrolyte and two layers of conductive polymer electrodes polymerized in situ on the electrolyte.

Figure 2 is a cyclic voltammogram curve of the integrated antifreeze supercapacitor prepared in Example 1 at different scan rates.

Figure 3 is the galvanostatic charge and discharge curves of the integrated antifreeze supercapacitor prepared in Example 1 under different current densities.

Figure 4 is a diagram of the integrated anti-freeze supercapacitor prepared in Example 1 supplying power to an electronic watch in a low-temperature tensile state, indicating that the integrated supercapacitor has good resistance to change and excellent anti-freeze performance.

Detailed ways

In order to make the above-mentioned objects, features and advantages of the present invention more obvious and understandable, the specific implementation modes of the present invention will be described in detail below in conjunction with the examples in the description.

Example 1:

Add 4.5g acrylamide, 2.8g nano-hydroxyapatite, 1.2g lithium chloride, 15mg N,N'-methylenebisacrylamide, 50mg potassium persulfate and 7g ethylene glycol to 6g deionized water and stir at 500rmp to mix. , ultrasonic at 0℃ for 10 minutes, ultrasonic power is 300W, polymerize at 85℃ for 3 hours to obtain antifreeze gel electrolyte; then soak the antifreeze gel electrolyte in aniline solution for 50 minutes, add ammonium persulfate and react for 60 minutes, so The mass ratio of aniline to ammonium persulfate is 2:5; finally, the conductive polymer composite gel electrolyte is cut around to obtain an integrated antifreeze supercapacitor. The cyclic voltammetry curves of the integrated antifreeze supercapacitor produced in this embodiment at different scan rates are shown in Figure 2, and the galvanostatic charge and discharge curves at different current densities are shown in Figure 3. In the low-temperature tensile state The electronic watch is powered as shown in Figure 4; the constant current charge and discharge test shows that the area specific capacitance of the integrated anti-freeze supercapacitor prepared in this embodiment is 366mF/cm ² at 25°C, and the device can operate at -20°C. Next work.

Example 2:

Add 4.1g acrylic acid, 2.6g nano-hydroxyapatite, 2.3g zinc chloride, 18mg N,N'-methylenebisacrylamide, 42mg ammonium persulfate and 3g glycerin to 10g deionized water, stir and mix at 300rmp, 3℃ Ultrasonicate for 8 minutes with an ultrasonic power of 250W and polymerize at 75°C for 2 hours to obtain an antifreeze gel electrolyte; then soak the antifreeze gel electrolyte in a pyrrole solution for 30 minutes, add potassium persulfate and react for 60 minutes, and the pyrrole and The mass ratio of potassium persulfate is 1:2; finally, the conductive polymer composite gel electrolyte is cut around to obtain an integrated antifreeze supercapacitor. The constant current charge and discharge test shows that the area specific capacitance of the integrated antifreeze supercapacitor produced in this embodiment is 343mF/cm ² at 25°C, but the device cannot operate at -20°C.

Example 3:

Add 5.2g polyethylene glycol, 3g nano-silica, 3.5g potassium chloride, 30mg polyethylene glycol diacrylate, 60mg potassium persulfate and 11g glycerin to 10g deionized water, stir and mix at 400rmp, and ultrasonic at 0°C 10 minutes, ultrasonic power is 300W, polymerize at 85°C for 3 hours to obtain an antifreeze gel electrolyte; then soak the antifreeze gel electrolyte in a pyrrole solution for 50 minutes, add ammonium persulfate and react for 60 minutes, the pyrrole and persulfate The mass ratio of ammonium is 1:3; finally, the conductive polymer composite gel electrolyte is cut around to obtain an integrated antifreeze supercapacitor. The constant current charge and discharge test shows that the area specific capacitance of the integrated antifreeze supercapacitor produced in this embodiment is 183mF/cm ² at 25°C, and the device can work at -20°C.

Example 4:

Add 3.6g acrylic acid, 2.1g nano-hydroxyapatite, 2.1g lithium chloride, 28mg polyethylene glycol diacrylate, 55mg potassium persulfate and 3g ethylene glycol to 12g deionized water, stir and mix at 600rmp, at 0°C Ultrasound for 11 minutes, with an ultrasonic power of 310W, and polymerize at 90°C for 6 hours to obtain an antifreeze gel electrolyte; then soak the antifreeze gel electrolyte in an aniline solution for 80 minutes, add ammonium persulfate, and react for 50 minutes. The aniline reacts with persulfate The mass ratio of ammonium sulfate is 1:1; finally, the conductive polymer composite gel electrolyte is cut around to obtain an integrated antifreeze supercapacitor. The constant current charge and discharge test shows that the area specific capacitance of the integrated antifreeze supercapacitor produced in this embodiment is 372mF/cm ² at 25°C, but the device cannot operate at -20°C.

Example 5:

Add 3.9g acrylamide, 1.9g nano-silica, 3.1g zinc chloride, 15mg N,N'-methylenebisacrylamide, 48mg ammonium persulfate and 9g ethylene glycol to 8g deionized water and stir at 550rmp to mix. Ultrasound for 18 minutes at 4°C, with an ultrasonic power of 180W, and polymerize at 95°C for 2 hours to obtain an antifreeze gel electrolyte; then soak the antifreeze gel electrolyte in an aniline solution for 70 minutes, add potassium persulfate and react for 70 minutes. The mass ratio of aniline to potassium persulfate is 3:5; finally, the conductive polymer composite gel electrolyte is cut around to obtain an integrated antifreeze supercapacitor. The constant current charge and discharge test shows that the area specific capacitance of the integrated antifreeze supercapacitor produced in this embodiment is 312mF/cm ² at 25°C, and the device can work at -20°C.

Example 6:

Add 6.4g polyethylene glycol, 3.3g nano-hydroxyapatite, 3g lithium chloride, 42mg polyethylene glycol diacrylate, 50mg ammonium persulfate and 9g ethylene glycol to 7g deionized water and stir at 450rmp to mix, 1 ℃, ultrasonic for 11 minutes, the ultrasonic power is 320W, polymerize at 88℃ for 3.5 hours to obtain an antifreeze gel electrolyte; then soak the antifreeze gel electrolyte in an aniline solution for 85 minutes, add ammonium persulfate and react for 65 minutes, the aniline The mass ratio to ammonium persulfate is 1:2; finally, the conductive polymer composite gel electrolyte is cut around to obtain an integrated antifreeze supercapacitor. The constant current charge and discharge test shows that the integrated antifreeze supercapacitor produced in this embodiment has an area specific capacitance of 283mF/cm ² at 25°C, and the device can work at -20°C.

Example 7:

Mix 4.9g acrylamide, 3g nano-hydroxyapatite, 2.2g lithium chloride, 18mg N,N'-methylenebisacrylamide, 46mg potassium persulfate and 2g glycerin with 10.5g deionized water at 580rmp, 0℃ Ultrasonic for 21 minutes, the ultrasonic power is 230W, polymerize at 92°C for 4 hours to obtain an antifreeze gel electrolyte; then soak the antifreeze gel electrolyte in a pyrrole solution for 80 minutes, add potassium persulfate and react for 65 minutes, the pyrrole and The mass ratio of potassium persulfate is 3:5; finally, the conductive polymer composite gel electrolyte is cut around to obtain an integrated antifreeze supercapacitor. The constant current charge and discharge test shows that the area specific capacitance of the integrated antifreeze supercapacitor produced in this embodiment is 362mF/cm ² at 25°C, but the device cannot operate at -20°C.

Claims (2)

1. The preparation method of the integrated anti-freezing supercapacitor is characterized by comprising the following steps of: (1) Adding 1-10 g of monomer, 1-10 g of nano particles, 1-10 g of electrolyte salt, 1-100 mg of cross-linking agent, 1-100 mg of initiator and 2-20 g of small molecular alcohol into 2-20 g of deionized water, stirring and blending, carrying out ultrasonic treatment at 0-5 ℃ for 1-30 minutes, carrying out polymerization at 50-120 ℃ for 1-10 hours to obtain an anti-freezing gel electrolyte; the monomer is polyethylene glycol, acrylamide or acrylic acid; the nano particles are nano silicon dioxide or nano hydroxyapatite; the electrolyte salt is lithium chloride, potassium chloride or zinc chloride; the cross-linking agent is N, N' -methylene bisacrylamide or polyethylene glycol diacrylate; the initiator is ammonium persulfate or potassium persulfate; the small molecular alcohol is ethylene glycol or glycerol; (2) Immersing the antifreeze gel electrolyte in a conductive polymer monomer solution for 10-150 minutes, and adding persulfate to react for 10-200 minutes, wherein the mass ratio of the conductive polymer monomer to the persulfate is 1-10:1-30; the conductive polymer monomer is aniline or pyrrole; the persulfate is ammonium persulfate or potassium persulfate; (3) Cutting the periphery of the conductive polymer composite gel electrolyte to obtain the integrated anti-freezing supercapacitor.

2. The integrated freeze resistant supercapacitor made by the method of claim 1.