An azo polymer fiber electrode and its application in fiber batteries

Abstract

The present invention discloses an azo polymer fiber electrode and its application in fiber batteries. The azo polymer fiber electrode is prepared by the following method: adding an acid solution and fibers to an azo polymer material, reacting in an environment of 20 - 75 °C for 2 - 7 days to obtain fibers with grown azo polymers, then washing with an organic solvent and drying at 20 - 75 °C for 12 - 72 hours to obtain the azo polymer fiber electrode. 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 the azo polymer material, the azo polymer material is more closely attached to the fiber, so that the electrochemical performance of the battery will not be significantly affected during deformation processes such as bending, folding, and stretching. The polymer fiber electrode of the present invention 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 more specifically, to an azo polymer fiber electrode and its application in fiber batteries. Background Art

[0002] Polymer electrodes, as a new type of electrode material, have attracted extensive 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 sourced, without the use of metal elements, and use light elements (C, N, O). Polymers have designability, so they can be designed to be most suitable for the application scenario according to different application scenarios. Polymer electrodes have the characteristics of light weight and flexibility, making 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 unique advantages in the field of flexible electronics, contributing to the realization of highly integrated and multifunctional electronic products.

[0003] Compared with traditional large-volume or planar-structured batteries, one-dimensional fiber-shaped batteries offer many advantages: 1) Fiber-shaped batteries show a high degree of compatibility with the current textile industry. Yarn is the basic element of current fabrics, and fiber-shaped batteries can be regarded as functional yarns and woven or knitted into energy textiles. 2) The fabrics woven or knitted with fiber-shaped batteries are breathable, capable of solving the problem of airtightness like leather in most planar-structured batteries. 3) Fiber-shaped batteries can be used to manufacture various flexible power sources, with unparalleled flexibility, compatibility, and miniaturization potential, providing multiple possibilities.

[0004] With the development of products such as smart watches, health monitoring devices, and smart clothing, there is an urgent social need for energy devices suitable for 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 sense of foreign body of users 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 for fields such as chronic disease management, elderly care, and rehabilitation medicine. Summary of the Invention

[0005] Conventional batteries have disadvantages such as large weight, lack of structural designability, and limited sources of metal elements. In view of this, regarding the current conventional inorganic metal electrodes, how to make them 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 a fiber battery prepared by the azo polymer electrode, so as to solve the problems of current inorganic metal electrodes.

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

[0007] An azo polymer fiber electrode is prepared by the following method: Add an acid solution and fibers to the azo polymer material, react in an environment of 20 - 75 °C for 2 - 7 days to obtain fibers growing with azo polymers, then wash with an organic solvent and dry at 20 - 75 °C for 12 - 72 hours to obtain the azo polymer fiber electrode; the azo polymer material is prepared by the following method: Dissolve a triazine derivative and a monomer with an azo group in a solvent, perform ultrasonic treatment, and dry to obtain the azo polymer material; the triazine derivative is 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde, trimethyl 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tribenzoate, 4,4',4''-((1,3,5-triazine-2,4,6-triyl)tri(oxy))tribenzaldehyde, or 4',4''',4'''''-(1,3,5-triazine-2,4,6-triyl)tri(([1,1'-biphenyl]-4-carbaldehyde)); the monomer with an azo group is 4,4'-dihydroxyazobenzene or 4,4'-diaminoazobenzene; the solvent is a mixed solution of mesitylene and ethanol, and the volume ratio of mesitylene 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:

[0011] (1) Add lithium hydroxide, ferrous sulfate, and phosphoric acid to a first solvent to prepare a reaction solution; after stirring for 0.5 - 6 hours, add the fibers to the reaction solution, and then perform a hydrothermal reaction; vacuum filter to collect the fibers, wash the fibers with a second solvent, and perform high-temperature treatment on the fibers after washing to obtain a positive electrode fiber electrode.

[0012] (2) Wrap a polymer separator around the azo polymer fiber electrode, and then wind the positive fiber electrode around the outside of the azo polymer fiber electrode wrapped with the polymer separator; then fill it into a plastic hollow tube, fill the electrolyte into the hollow tube in an inert gas atmosphere, and encapsulate the battery with glue to obtain an azo polymer fiber battery.

[0013] 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, glacial acetic acid; the second solvent is one or a mixture of acetonitrile, chloroform, methanol, deionized water, ethanol; the fiber is at least one of glass fiber, carbon fiber, plastic fiber; the conditions for the hydrothermal reaction are calcination at 120-200 °C for 6-12 hours; the conditions for the high-temperature treatment are calcination at 450-800 °C for 6-12 hours.

[0014] Compared with the prior art, the present invention has the following beneficial effects:

[0015] (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 closely attached to the fiber, so that the electrochemical performance of the battery is not significantly affected during deformation processes such as bending, folding, and stretching. The polymer fiber electrode of the present invention does not contain metal elements and has more excellent electrochemical performance under the same mass.

[0016] (2) Azo polymers are a class of polymers with azo groups. Introducing azo groups into the polymer enables the polymer to better embed metal ions, greatly increasing the capacity of the battery. Moreover, it has good electrochemical stability, and its structure can remain unchanged during long-term charge and discharge processes, greatly extending the cycle life of the battery. Azo polymers can grow tightly on the fibers. Using it as the active material of the fiber battery, the preparation process is simple, the process is streamlined, and the electrochemical performance of the prepared azo polymer fiber battery is not affected during deformation processes such as bending, folding, and stretching when made into a device. Description of the Drawings

[0017] Figure 1 It is the infrared spectrum of the azo polymer powder in Example 1;

[0018] Figure 2 It is the Raman spectrum of the azo polymer powder in Example 1;

[0019] Figure 3 It is the solid nuclear magnetic map of the azo polymer powder in Example 1;

[0020] Figure 4 Scanning electron micrograph of the azo polymer fiber electrode of Example 1;

[0021] Figure 5 Rate performance of the lithium iron phosphate battery of the azo polymer fiber battery of Example 3;

[0022] Figure 6 Cycle performance of the lithium iron phosphate battery of the azo polymer fiber battery of Example 3;

[0023] Figure 7 Schematic diagram of the preparation process of the azo polymer fiber battery;

[0024] Figure 8 Physical picture of the azo polymer fiber battery. Specific implementation mode

[0025] The temperature parameters in the present invention, without special limitation, allow both constant temperature treatment and treatment within a certain temperature range. The constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument.

[0026] The "azo polymer fiber electrode" in the present invention refers to a fibrous electrode as shown in Figure 4 .

[0027] The "azo polymer fiber battery" in the present invention refers to a battery with a fibrous macroscopic form as shown in Figure 8 .

[0028] Without special instructions, the frequency of the "ultrasonic treatment" in the present invention is 20 - 100 kHz, and the time is 30 - 300 min.

[0029] Example 1: Preparation of azo polymer fiber electrode

[0030] Add 4,4',4''-(1,3,5-triazine-2,4,6-triyl) tribenzaldehyde (28 mg), 4,4'-diaminoazobenzene (33.6 mg) and mesitylene / ethanol (1:1 v / v, 20 mL). Ultrasonically treat the mixture for 300 minutes to disperse it evenly to obtain an azo polymer material. Subsequently, add carbon fibers with a length of 15 cm that have been washed, and ultrasonically treat the mixture for 300 minutes to disperse it evenly. Subsequently, slowly add acetic acid (5 mol·L -1 , 1.2 mL). Seal and react at room temperature for 5 days. Take out the carbon fibers on which the azo polymer has grown, and wash them with deionized water and dichloromethane respectively. Vacuum dry at 75 °C for 24 hours.

[0031] Example 2: Preparation of azo polymer fiber electrode

[0032] Trimethyl 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tribenzoate (28 mg), azobenzene-4,4-dicarboxylic acid (33.6 mg) and mesitylene / ethanol (1:2 v / v, 20 mL) were taken. The mixture was sonicated for 300 minutes to disperse it evenly. Subsequently, acetic acid (5 mol·L -1 , 1.2 mL) was slowly added. Then the vial was sealed and reacted at room temperature for 5 days. The carbon fiber on which the azo polymer grew was taken out and washed with deionized water and dimethyl sulfoxide respectively. It was dried in vacuo at 75 °C for 24 hours.

[0033] Example 3: Preparation of azo polymer fiber battery

[0034] Lithium hydroxide (40 mg), ferrous sulfate (90 mg) and phosphoric acid (36 mg) were added to ethylene glycol. After stirring for 2 hours, the washed carbon fiber with a length of 15 cm was added. The hydrothermal solution and the carbon fiber were transferred to a reaction kettle and subjected to hydrothermal reaction at 180 °C for 10 hours. Then it was calcined at 650 °C for 8 hours in a nitrogen atmosphere to obtain a positive fiber electrode. The azo polymer fiber electrode obtained in Example 1 was wrapped with a polymer separator on the periphery, and then the positive fiber electrode was wound outside the azo polymer fiber electrode wrapped with the polymer separator; then it was filled in a plastic hollow tube, and the hollow tube was filled with electrolyte in an inert gas atmosphere, and the battery was sealed with glue to obtain an azo polymer electrode fiber battery. The schematic diagram of the preparation process of the azo polymer fiber battery is as Figure 7 shown.

[0035] Performance test

[0036] The infrared spectrum, Raman spectrum and solid nuclear magnetic of the azo polymer powder were tested.

[0037] The surface morphology of the azo polymer electrode was tested and characterized.

[0038] The rate performance and cycle performance of the azo polymer fiber battery were tested.

[0039] The test results of the rate performance of the azo polymer fiber battery obtained in Example 3 are shown in Table 1.

[0040]

[0041] 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.

[0042] Figure 1 is the infrared spectrum diagram of the azo polymer powder of Example 1. FromFigure 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 appeared in the polymer. Substance A is 4,4',4''-(1,3,5-triazine-2,4,6-triyl) tribenzaldehyde, and substance B is 4,4'-diaminoazobenzene.

[0043] Figure 2 It is the Raman spectrogram of the azo polymer powder of Example 1. From Figure 2 it can be seen that the azo polymer contains C-N, N=N and C=N, indicating the successful synthesis of the azo polymer.

[0044] Figure 3 It is the solid nuclear magnetic spectrogram of the azo polymer powder of Example 1. From Figure 3 it can be clearly seen that the azo polymer was successfully prepared.

[0045] Figure 4 It is the scanning electron micrograph of the azo polymer fiber electrode of Example 1. From Figure 4 it can be seen that the azo polymer adheres tightly to the surface of the carbon fiber.

[0046] Figure 5 It is the rate performance of the lithium iron phosphate battery of the azo polymer fiber battery of Example 3. From Figure 5 it can be seen that the azo polymer fiber battery has excellent electrochemical performance and a high battery capacity.

[0047] Figure 6 It is the cycle performance of the lithium iron phosphate battery of the azo polymer fiber battery of Example 3. From 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 change during long-term use.

[0048] Figure 7 It is the schematic diagram of the preparation of the azo polymer fiber battery.

[0049] Figure 8 It is the physical picture of the azo polymer fiber battery.

Claims

1. An azo polymer fiber battery, characterized in that It is prepared by the following method: (1) Add lithium hydroxide, ferrous sulfate and phosphoric acid into a first solvent to prepare a reaction solution; after stirring for 0.5 to 6 hours, add fibers into the reaction solution, and then carry out a hydrothermal reaction; collect the fibers by vacuum filtration, wash the fibers with a second solvent, and after the washing is completed, perform high-temperature treatment on the fibers to obtain a positive fiber electrode; (2) Wrap a layer of polymer separator around the azo polymer fiber electrode, and then wind the positive fiber electrode around the outside of the polymer fiber electrode wrapped with the polymer separator; then fill it into a plastic hollow tube, fill the electrolyte into the hollow tube in an inert gas atmosphere, and encapsulate the battery with glue to obtain an azo polymer electrode fiber battery; The azo polymer fiber electrode is prepared by the following method: add an acid solution and fibers to an azo polymer material, react at 20 to 75 °C for 2 to 7 days to obtain fibers growing azo polymer, and then wash with an organic solvent and dry 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: dissolve a triazine derivative and a monomer with an azo group in a solvent, perform ultrasonic treatment, and dry to obtain an azo polymer material; the triazine derivative is 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde, trimethyl 4,4',4''-(1,3,5-triazine-2,4,6-triyl)tribenzoate, 4,4',4''-((1,3,5-triazine-2,4,6-triyl)tris(oxy))tribenzaldehyde or 4',4''',4'''''-(1,3,5-triazine-2,4,6-triyl)tris(([1,1'-biphenyl]-4-carbaldehyde)); the monomer with an azo group is 4,4'-dihydroxyazobenzene or 4,4'-diaminoazobenzene; the solvent is a mixed solution of mesitylene and ethanol, and the volume ratio of mesitylene to ethanol is 1:0.5 to 3.

2.

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

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

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