Azo polymer fiber electrode and fiber battery application

Abstract

The invention discloses an azo polymer fiber electrode and fiber battery application, and the azo polymer fiber electrode is prepared by the following method: adding an acid solution and fibers into an azo polymer material, reacting for 2-7 days in an environment of 20-75 DEG C to obtain fibers on which azo polymers grow, cleaning with an organic solvent, and drying to obtain the azo polymer fiber electrode. And drying at 20-75 DEG C for 12-72 hours to obtain the azo polymer fiber electrode. According to the polymer fiber electrode disclosed by the invention, the azo polymer material is adopted as an active material of the electrode, and the azo polymer material is more tightly attached to the fiber by using the fiber electrode loaded with the azo polymer material, so that the electrochemical performance of the battery is not obviously influenced in the deformation processes of bending, folding, stretching and the like. The polymer fiber electrode does not contain metal elements, and has more excellent electrochemical performance under the same mass.

Description

Technical Field

[0001] The present invention relates to the technical field of fiber batteries, and in particular to an azo polymer fiber electrode and fiber battery applications. Background Art

[0002] Polymer electrodes, as a new type of electrode material, have attracted widespread attention in the field of energy storage and conversion in recent years. Compared with traditional metal inorganic electrodes, polymer electrodes have flexible structural designability, light weight, rich elements and environmental friendliness. The raw materials of polymer electrodes are widely available, and no metal elements are required, but lightweight elements (C, N, O) are used. Polymers are designable, so the most suitable design for the application scenario can be made according to different application scenarios. Polymer electrodes are lightweight and flexible, which makes them have broad application prospects in portable electronic devices, wearable devices and flexible electronics. Compared with traditional metal inorganic electrodes, the electrochemical performance of polymer electrodes will not be significantly affected during deformation processes such as bending, folding and stretching. This gives polymer electrodes a unique advantage in the field of flexible electronics, which helps to realize highly integrated and multifunctional electronic products.

[0003] Compared with traditional large-volume or planar structure batteries, one-dimensional fiber-shaped batteries offer many advantages: 1) Fiber-shaped batteries show high compatibility with the current textile industry. Yarn is the basic element of current fabrics, and fiber-shaped batteries can be considered as functional yarns and woven or knitted into energy textiles. 2) Fabrics woven or knitted by fiber-shaped batteries are breathable, which can solve the problem that most planar structure batteries are leather-like and non-breathable. 3) Fiber-shaped batteries can be used to manufacture a variety of flexible power sources with unparalleled flexibility, compatibility and miniaturization potential, providing a variety of possibilities.

[0004] With the development of products such as smart watches, health monitoring devices, and smart clothing, society urgently needs energy devices that adapt to them. The flexibility and lightness of fiber batteries make them an ideal power source for such devices. Fiber batteries can be integrated with clothing or other textiles, reducing the user's foreign body sensation and improving comfort. In the medical field, the application of fiber batteries provides power for wearable medical devices, making continuous monitoring and remote treatment possible. This is of great significance to fields such as chronic disease management, elderly care, and rehabilitation medicine. Summary of the invention

[0005] Conventional batteries have the disadvantages of being heavy, not structurally designable, and having limited sources of metal elements. In view of this, with regard to the current conventional inorganic metal electrodes, how to match more substrate materials and change the macroscopic morphology of the battery, the purpose of the present invention is to provide an azo polymer material and an azo polymer fiber electrode prepared therefrom, and to prepare a fiber battery through the azo polymer electrode, so as to solve the current problems of inorganic metal electrodes.

[0006] To achieve the above objectives, the present invention adopts the following technical solutions.

[0007] An azo polymer fiber electrode is prepared by the following method: adding acid solution and fiber to an azo polymer material, reacting for 2 to 7 days under an environment of 20 to 75°C to obtain fibers growing azo polymers, then washing with an organic solvent, and drying at 20 to 75°C for 12 to 72 hours to obtain an azo polymer fiber electrode; the azo polymer material is prepared by the following method: dissolving a triazine derivative and a monomer with an azo group in a solvent, ultrasonically treating, and drying to obtain the azo polymer material; the triazine derivative is 4,4',4''-(1,3,5-triazine-2,4,6-triyl) tribenzaldehyde, 4,4',4''-(1,3,5-triazine-2,4,6-triyl) tribenzoic acid trimethyl ester, 4,4', 4''-((1,3,5-triazine-2,4,6-triyl)tri(oxyl))tribenzaldehyde or 4',4''',4'''''-(1,3,5-triazine-2,4,6-triyl)tris(([1,1'-biphenyl]-4-carboxaldehyde)); the monomer with an azo group is 4,4'-dihydroxyazobenzene or 4,4'-diaminoazobenzene; the solvent is a mixed solution of trimethylbenzene and ethanol, and the volume ratio of trimethylbenzene to ethanol is 1:0.5-3.2.

[0008] Preferably, the fiber is at least one of glass fiber, carbon fiber and plastic fiber.

[0009] Preferably, the organic solvent is tetrahydrofuran, acetone, dichloromethane, ethyl acetate, dimethyl sulfoxide, N-methylpyrrolidone or trifluoroacetic acid.

[0010] An azo polymer fiber battery is prepared by the following method: (1) adding lithium hydroxide, ferrous sulfate and phosphoric acid to a first solvent to prepare a reaction solution; after stirring for 0.5 to 6 hours, adding fibers to the reaction solution, and then performing a hydrothermal reaction; collecting the fibers by vacuum filtration, washing the fibers with a second solvent, and performing a high temperature treatment on the fibers after washing to obtain a positive fiber electrode; (2) Wrapping the azo polymer fiber electrode with a layer of polymer separator, and then winding the positive electrode fiber electrode around the outside of the azo polymer fiber electrode wrapped with the polymer separator; then filling it in a plastic hollow tube, filling the hollow tube with electrolyte in an inert gas atmosphere, and using glue to encapsulate the battery to obtain an azo polymer fiber battery.

[0011] Preferably, the mass ratio of lithium hydroxide, ferrous sulfate and phosphoric acid is 1-2:1.5-5:1; the first solvent is one or a mixture of ethanol, deionized water, ethylene glycol, glycerol and glacial acetic acid; the second solvent is one or a mixture of acetonitrile, chloroform, methanol, deionized water and ethanol; the fiber is at least one of glass fiber, carbon fiber and plastic fiber; the condition of the hydrothermal reaction is calcination at 120-200°C for 6-12 hours; the condition of the high temperature treatment is calcination at 450-800°C for 6-12 hours.

[0012] Compared with the prior art, the present invention has the following beneficial effects: (1) The polymer fiber electrode of the present invention uses an azo polymer material as the active material of the electrode. By using a fiber electrode loaded with an azo polymer material, the azo polymer material is more tightly attached to the fiber, so that the electrochemical performance of the battery will not be significantly affected during deformation such as bending, folding, and stretching. The polymer fiber electrode of the present invention does not contain metal elements and has better electrochemical performance at the same quality.

[0013] (2) Azo polymers are a type of polymers with azo groups. Introducing azo groups into polymers allows the polymers to better embed metal ions, which greatly increases the capacity of the battery. It also has good electrochemical stability, and its structure can remain intact during long-term charging and discharging, which greatly extends the cycle life of the battery. Azo polymers can grow tightly on fibers, and using them as active materials for fiber batteries has a simple preparation process and streamlined procedures. When the prepared azo polymer fiber battery is made into a device, its electrochemical performance will not be affected during deformation processes such as bending, folding, and stretching. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 is the infrared spectra of the azo polymer powder of Example 1; Figure 2 is a Raman spectrum of the azo polymer powder of Example 1; Figure 3 is the solid NMR image of the azo polymer powder of Example 1; Figure 4 is a scanning electron microscope image of the azo polymer fiber electrode of Example 1; Figure 5 The lithium iron phosphate battery rate performance of the azo polymer fiber battery of Example 3; Figure 6 The lithium iron phosphate battery cycle performance of the azo polymer fiber battery of Example 3; Figure 7 This is a schematic diagram of the preparation process of azo polymer fiber batteries; Figure 8 This is a physical picture of azo polymer fiber battery. DETAILED DESCRIPTION

[0015] The temperature parameters in the present invention, if not specifically limited, allow for both constant temperature treatment and treatment within a certain temperature range. The constant temperature treatment allows the temperature to fluctuate within the precision range controlled by the instrument.

[0016] The "azo polymer fiber electrode" in the present invention refers to Figure 4 A fiber-shaped electrode is shown in FIG.

[0017] The "azo polymer fiber battery" in the present invention refers to Figure 8 One macroscopic form shown in FIG is a fiber-shaped battery.

[0018] Unless otherwise specified, the frequency of "ultrasonic treatment" in the present invention is 20-100 kHz and the time is 30-300 min.

[0019] Example 1: Preparation of azo polymer fiber electrodes 4,4',4''-(1,3,5-triazine-2,4,6-triyl) tribenzaldehyde (28 mg), 4,4'-diaminoazobenzene (33.6 mg) and trimethylol / ethanol (1:1 v / v, 20 mL) were ultrasonically treated for 300 minutes to disperse them uniformly to obtain an azo polymer material. Then, 15 cm long cleaned carbon fiber was added and the mixture was ultrasonically treated for 300 minutes to disperse them uniformly. Then, acetic acid (5 mol·L -1 , 1.2 mL). Seal and react at room temperature for 5 days. Take out the carbon fiber with grown azo polymer, wash it with deionized water and dichloromethane respectively. Dry it in vacuum at 75 °C for 24 hours.

[0020] Example 2: Preparation of azo polymer fiber electrodes 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tribenzoic acid trimethyl ester (28 mg), azobenzene-4,4-dicarboxylic acid (33.6 mg) and trimethylbenzene / ethanol (1:2 v / v, 20 mL) were ultrasonically treated for 300 minutes to make the mixture uniformly dispersed. Then acetic acid (5 mol·L-1 , 1.2 mL). Then seal the vial and react at room temperature for 5 days. Take out the carbon fiber with grown azo polymer, wash it with deionized water and dimethyl sulfoxide respectively, and vacuum dry it at 75 ℃ for 24 hours.

[0021] Example 3: Preparation of azo polymer fiber battery Lithium hydroxide (40 mg), ferrous sulfate (90 mg) and phosphoric acid (36 mg) were added to ethylene glycol, and after stirring for 2 hours, 15 cm long washed carbon fibers were added. The hydrothermal liquid and carbon fibers were transferred to a reactor and subjected to a hydrothermal reaction at 180 °C for 10 hours. Then calcined at 650 °C in a nitrogen atmosphere for 8 hours to obtain a positive fiber electrode. Wrap a layer of polymer diaphragm around the azo polymer fiber electrode obtained in Example 1, and then wrap the positive fiber electrode around the outside of the azo polymer fiber electrode wrapped with the polymer diaphragm; then fill it in a plastic hollow tube, fill the hollow tube with electrolyte in an inert gas atmosphere, and seal the battery with glue to obtain an azo polymer electrode fiber battery. The schematic diagram of the preparation process of the azo polymer fiber battery is shown in the figure. Figure 7 shown. Performance Testing

[0022] The infrared spectrum, Raman spectrum and solid-state NMR of azo polymer powder were tested.

[0023] The surface morphology of the azo polymer electrode was tested and characterized.

[0024] Test the rate performance and cycle performance of azo polymer fiber batteries.

[0025] The rate performance test results of the azo polymer fiber battery obtained in Example 3 are shown in Table 1.

[0026]

[0027] Conclusion: The data in Table 1 show that the azo polymer fiber battery obtained in Example 3 has a higher capacity and can store more energy. The azo polymer electrode has good flexibility and stability and is suitable for fiber batteries.

[0028] Figure 1 is the infrared spectrum of the azo polymer powder of Example 1, from Figure 1 It can be seen that the azo polymer was successfully synthesized, the characteristic peaks of the two raw materials disappeared, and new characteristic peaks of the polymer were generated. Substance A is 4,4',4''-(1,3,5-triazine-2,4,6-triyl) tribenzaldehyde, and substance B is 4,4'-diaminoazobenzene.

[0029] Figure 2 is the Raman spectrum of the azo polymer powder of Example 1, from Figure 2 It can be seen that the azo polymer contains CN, N=N and C=N, indicating the successful synthesis of the azo polymer.

[0030] Figure 3 is the solid NMR image of the azo polymer powder of Example 1, from Figure 3 It can be clearly seen that the azo polymer was successfully prepared.

[0031] Figure 4 is a scanning electron microscope image of the azo polymer fiber electrode of Example 1, Figure 4 It can be seen that the azo polymer is tightly attached to the surface of the carbon fiber.

[0032] Figure 5 The lithium iron phosphate battery rate performance of the azo polymer fiber battery of Example 3 is as follows: Figure 5 It can be seen that the azo polymer fiber battery has excellent electrochemical properties and high battery capacity.

[0033] Figure 6 The lithium iron phosphate battery cycle performance of the azo polymer fiber battery of Example 3 is shown in FIG. Figure 6 It can be seen that the azo polymer fiber battery has an excellent cycle life and can maintain the battery capacity without significant changes during long-term use.

[0034] Figure 7 Schematic diagram of the preparation of azo polymer fiber batteries.

[0035] Figure 8 This is a physical picture of the azo polymer fiber battery.

Claims

1. An azo polymer fiber electrode, characterized in that The azo polymer material is prepared by the following method: adding acid solution and fiber to an azo polymer material, reacting for 2 to 7 days under an environment of 20 to 75°C to obtain fibers of grown azo polymers, then washing with an organic solvent, and drying at 20 to 75°C for 12 to 72 hours to obtain an azo polymer fiber electrode; the azo polymer material is prepared by the following method: dissolving a triazine derivative and a monomer with an azo group in a solvent, ultrasonically treating, and drying to obtain an azo polymer material; the triazine derivative is 4,4',4''-(1,3,5-triazine-2,4,6-triyl) tribenzaldehyde, 4,4',4''-(1,3,5-triazine-2,4,6-triyl) tribenzoic acid trimethyl ester, 4,4', 4''-((1,3,5-triazine-2,4,6-triyl)tri(oxyl))tribenzaldehyde or 4',4''',4'''''-(1,3,5-triazine-2,4,6-triyl)tris(([1,1'-biphenyl]-4-carboxaldehyde)); the monomer with an azo group is 4,4'-dihydroxyazobenzene or 4,4'-diaminoazobenzene; the solvent is a mixed solution of trimethylbenzene and ethanol, and the volume ratio of trimethylbenzene to ethanol is 1:0.5-3.

2.

2. The azo polymer fiber electrode according to claim 1, characterized in that The fiber is at least one of glass fiber, carbon fiber and plastic fiber.

3. The azo polymer fiber electrode according to claim 1, characterized in that The organic solvent is tetrahydrofuran, acetone, dichloromethane, ethyl acetate, dimethyl sulfoxide, N-methylpyrrolidone or trifluoroacetic acid.

4. An azo polymer fiber battery, characterized in that Prepared by the following method: (1) adding lithium hydroxide, ferrous sulfate and phosphoric acid to a first solvent to prepare a reaction solution; after stirring for 0.5 to 6 hours, adding fibers to the reaction solution, and then performing a hydrothermal reaction; collecting the fibers by vacuum filtration, washing the fibers with a second solvent, and performing a high temperature treatment on the fibers after washing to obtain a positive fiber electrode; (2) Wrapping the azo polymer fiber electrode according to claim 1 with a layer of polymer separator, and then winding the positive electrode fiber electrode around the outside of the polymer fiber electrode wrapped with the polymer separator; then filling it in a plastic hollow tube, filling the hollow tube with electrolyte in an inert gas atmosphere, and packaging the battery with glue to obtain an azo polymer electrode fiber battery.

5. The azo polymer fiber battery according to claim 4, characterized in that: The mass ratio of lithium hydroxide, ferrous sulfate and phosphoric acid is 1-2:1.5-5:1; the first solvent is one or a mixture of ethanol, deionized water, ethylene glycol, glycerol and glacial acetic acid; the second solvent is one or a mixture of acetonitrile, chloroform, methanol, deionized water and ethanol; the fiber is at least one of glass fiber, carbon fiber and plastic fiber; the condition of the hydrothermal reaction is calcination at 120-200°C for 6-12 hours; the condition of the high temperature treatment is calcination at 450-800°C for 6-12 hours.

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