Flexible wearable friction nanogenerator friction layer material based on apes modification pan and preparation method

Abstract

The application discloses a flexible wearable friction nanogenerator friction layer material based on APTES modified PAN and a preparation method, relates to the field of flexible wearable friction nanogenerator, and solves the problems of short endurance time of existing wearable electronic equipment, complex preparation process, high cost, poor performance and low working stability in practical application. The preparation method comprises the following steps: dissolving polyacrylonitrile in an N,N-dimethylformamide solution, heating and stirring to obtain a high polymer precursor; adding 3-aminopropyl triethoxysilane into the high polymer precursor and uniformly stirring to obtain a spinning solution; preparing the spinning solution into a nanofiber film through an electrostatic spinning process; and drying the prepared nanofiber film to obtain a friction layer. The application is also suitable for the preparation experiment of the flexible wearable friction nanogenerator friction layer material of the polyacrylonitrile nanofiber film.

Description

Technical Field

[0001] This invention relates to the field of flexible wearable triboelectric nanogenerator technology. Background Technology

[0002] In recent years, with the continuous advancement of technology, a large number of wearable electronic devices have been applied to the human body, and their numbers continue to grow rapidly. These electronic devices are widely used in health monitoring, the Internet of Things, artificial intelligence, and wireless sensing, greatly facilitating and enriching people's lives. However, wearable electronic devices often require frequent charging or battery replacements, limiting their development towards miniaturization, intelligent functionality, and wireless mobility. Therefore, there is an urgent need for a new way to charge these electronic devices to extend their battery life and further realize self-powered wearable electronic devices.

[0003] Triboelectric nanogenerators can convert low-frequency, disordered, and weak kinetic energy in daily life into alternating electrical energy, thus serving as an energy source to power wearable electronic devices. However, in practical applications, developing flexible wearable triboelectric nanogenerators that are simple to fabricate, inexpensive, high-performing, and stable remains a significant challenge. Summary of the Invention

[0004] The purpose of this invention is to solve the problems of short battery life, complex manufacturing process, high cost, poor performance, and low stability of existing wearable electronic devices in practical applications.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] Option 1: A method for preparing a flexible wearable triboelectric nanogenerator friction layer material based on APTES-modified PAN, comprising the following steps:

[0007] S1. Polyacrylonitrile is dissolved in N,N-dimethylformamide solution and heated and stirred to obtain polymer precursor;

[0008] S2. Add 3-aminopropyltriethoxysilane to the polymer precursor and stir until homogeneous to obtain a spinning solution;

[0009] S3. Nanofiber films are prepared from spinning solution by electrospinning process;

[0010] S4. The prepared nanofiber film is dried to obtain the friction layer material.

[0011] Furthermore, a preferred embodiment is provided, wherein the polymer obtained in S1 is polyacrylonitrile, polyvinylidene fluoride, or polytetrafluoroethylene.

[0012] Furthermore, a preferred embodiment is provided, wherein the solvent in the N,N-dimethylformamide solution in S1 is water, ethanol, N,N-dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone.

[0013] Furthermore, a preferred embodiment is provided in which the polymer concentration in the N,N-dimethylformamide solution in S1 is 5-20 wt% by mass.

[0014] Furthermore, a preferred embodiment is provided in which the heating temperature in S1 is 50°C-90°C.

[0015] Option 2: A flexible triboelectric nanogenerator friction layer material based on APTES-modified PAN, wherein the friction layer material is prepared by any one of the methods described in Option 1.

[0016] Option 3: A method for preparing a flexible triboelectric nanogenerator based on the above-described option, comprising a first conductive electrode layer, a first friction layer, a second friction layer, and a second conductive electrode layer stacked sequentially, wherein the second friction layer is the friction layer material of the flexible triboelectric nanogenerator based on APTES-modified PAN as described in Option 2.

[0017] Furthermore, a preferred embodiment is provided, wherein the second friction layer is polyethylene terephthalate, thermoplastic polyurethane elastomer, polytetrafluoroethylene, or nylon 66.

[0018] Furthermore, a preferred embodiment is provided in which the materials of the first conductive electrode layer and the second conductive electrode layer are gold, silver, aluminum, iron, copper, carbon nanotubes, graphene, or fullerene.

[0019] Furthermore, a preferred embodiment is provided in which the thickness of both the first conductive electrode layer and the second conductive electrode layer is in the range of 60-100 μm.

[0020] The advantages of this invention are:

[0021] This invention provides a friction layer material and preparation method for a flexible wearable triboelectric nanogenerator based on APTES-modified PAN. By modifying the friction material, the triboelectric charging capability is improved, thereby significantly enhancing the output performance of the triboelectric nanogenerator.

[0022] Test results show that the triboelectric nanogenerator described in this invention can achieve an output voltage of 404.1V, which is 2.33 times higher than that of the unmodified PAN fiber film.

[0023] This invention is also applicable to the preparation experiments of friction layer materials for flexible wearable triboelectric nanogenerators made of polyacrylonitrile nanofiber films. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of the structure of the triboelectric nanogenerator in the preparation method of the flexible triboelectric nanogenerator based on the above scheme described in Embodiment 7.

[0025] Figure 2 This is a transmission electron microscope image of PANA from Example 1.

[0026] Figure 3 These are the X-ray diffraction patterns of PANA in Example 1 and PAN in Comparative Example 1.

[0027] Figure 4 These are the X-ray photoelectron spectra of N1s of PANA in Example 1 and PAN in Comparative Example 1.

[0028] Figure 5 These are the X-ray photoelectron spectra of Si1s of PANA in Example 1 and PAN in Comparative Example 1.

[0029] Figure 6 The diagram shows the voltage output performance of the triboelectric nanogenerator based on PANA in Example 1 and PAN in Comparative Example 1.

[0030] Figure 7 This is a voltage output performance diagram of the PANA-based triboelectric nanogenerator in Example 1 under different pressures.

[0031] Figure 8 This is a voltage output performance diagram of the PANA-based triboelectric nanogenerator in Example 1 at different distances.

[0032] Figure 9 This is a graph showing the voltage output performance of the PANA-based triboelectric nanogenerator in Example 1 at different frequencies.

[0033] Figure 10 This is a voltage output performance diagram of the PANA-based flexible triboelectric nanogenerator in Example 1 under multiple cycles of contact and separation.

[0034] Figure 1 In the middle, there is a first conductive electrode layer 1, a first friction layer 2, a second friction layer 3, and a second conductive electrode layer 4. Detailed Implementation

[0035] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them.

[0036] Implementation Method 1: This implementation method provides a method for preparing a friction layer material for a flexible wearable triboelectric nanogenerator based on APTES-modified PAN, including the following steps:

[0037] S1. Polyacrylonitrile is dissolved in N,N-dimethylformamide solution and heated and stirred to obtain polymer precursor;

[0038] S2. Add 3-aminopropyltriethoxysilane to the polymer precursor and stir until homogeneous to obtain a spinning solution;

[0039] S3. Nanofiber films are prepared from spinning solution by electrospinning process;

[0040] S4. The prepared nanofiber film is dried to obtain the friction layer material.

[0041] This embodiment proposes a method for preparing a friction layer material for a flexible wearable triboelectric nanogenerator based on APTES-modified PAN. By modifying the friction material, the triboelectric charging capability is changed, thereby significantly improving the output performance of the triboelectric nanogenerator.

[0042] Implementation Method 2: This implementation method further defines the preparation method of the friction layer material of the flexible wearable triboelectric nanogenerator based on APTES modified PAN as described in Implementation Method 1. The polymer obtained in S1 is one of polyacrylonitrile, polyvinylidene fluoride, and polytetrafluoroethylene.

[0043] In this embodiment, the polymer in the solution of S1 can be polyacrylonitrile, polyvinylidene fluoride, or polytetrafluoroethylene.

[0044] Implementation Method 3: This implementation method further defines the preparation method of the friction layer material of the flexible wearable triboelectric nanogenerator based on APTES modified PAN as described in Implementation Method 1. The solvent in the N,N-dimethylformamide solution in S1 is one of water, ethanol, N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.

[0045] In this embodiment S1, the solvent in the solution can be water, ethanol, N,N-dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone.

[0046] Implementation Method 4: This implementation method further defines the preparation method of the friction layer material of the flexible wearable triboelectric nanogenerator based on APTES modified PAN as described in Implementation Method 1. The polymer concentration in the N,N-dimethylformamide solution in S1 is 5-20 wt% by mass.

[0047] Implementation Method 5: This implementation method further defines the preparation method of the friction layer material of the flexible wearable triboelectric nanogenerator based on APTES modified PAN as described in Implementation Method 1. The heating temperature in S1 is 50℃-90℃.

[0048] In this embodiment, the mass percentage of 3-aminopropyltriethoxysilane in the solution S2 is 5-15 wt%.

[0049] Preferably, the electrospinning conditions in S3 are: voltage of 15-25kV, roller speed of 60-120rpm, distance between the syringe and the roller surface of 10-20cm, and injection rate of the spinning solution of 0.5-2mL / h.

[0050] Preferably, the electrospinning time in S3 is 1-12 hours.

[0051] Preferably, the drying temperature in S4 is 80-120 degrees Celsius.

[0052] Preferably, the drying time in S4 is 10-18 hours.

[0053] Implementation Method Six: This implementation method proposes a friction layer material for a flexible triboelectric nanogenerator based on APTES-modified PAN. The friction layer material is prepared by the method described in any one of Implementation Methods One to Five.

[0054] Implementation Method Seven: This implementation method proposes a method for preparing a flexible triboelectric nanogenerator based on the above scheme, comprising a first conductive electrode layer 1, a first friction layer 2, a second friction layer 3, and a second conductive electrode layer 4 stacked sequentially, wherein the second friction layer 3 is the friction layer material of the flexible triboelectric nanogenerator based on APTES modified PAN as described in Implementation Method Six.

[0055] Test results show that the triboelectric nanogenerator described in this invention can achieve an output voltage of 404.1V, which is 2.33 times higher than that of the unmodified PAN fiber film.

[0056] Implementation Method 8: This implementation method is a preparation method of the flexible triboelectric nanogenerator based on the above scheme described in Implementation Method 7. The second friction layer 3 is polyethylene terephthalate, thermoplastic polyurethane elastomer, polytetrafluoroethylene, or nylon 66.

[0057] The material of the second friction layer described in this embodiment cannot be the same as the material of the first friction layer.

[0058] Implementation Method Nine: This implementation method further defines the preparation method of the flexible triboelectric nanogenerator based on the above scheme described in Implementation Method Seven. The materials of the first conductive electrode layer 1 and the second conductive electrode layer 4 are gold, silver, aluminum, iron, copper, carbon nanotubes, graphene, or fullerene.

[0059] The material selected for the first conductive electrode layer 1 in this embodiment is any one of gold, silver, aluminum, iron, copper, carbon nanotubes, graphene or fullerene, and the material of the second conductive electrode layer 4 is any one of the materials selected for the first conductive electrode layer 1; and the number of materials selected for each conductive electrode layer is not unique. The first conductive electrode layer 1 and the second conductive electrode layer 4 can be the same material, different materials, or an alloy of any two materials.

[0060] Implementation Method 10: This implementation method further defines the preparation method of the flexible triboelectric nanogenerator based on the above scheme described in Implementation Method 7. The thickness of the first conductive electrode layer 1 and the second conductive electrode layer 4 are both in the range of 60-100 μm.

[0061] The first conductive electrode layer 1 and the second conductive electrode layer 4 described in this embodiment can have different values ​​in the range of 60-100 μm.

[0062] Implementation Method Eleven: This implementation method is a detailed explanation of Implementation Methods One through Ten described above.

[0063] In this embodiment, both the first conductive electrode layer 1 and the second conductive electrode layer 4 are copper electrode layers, the first friction layer 2 is made of PET film material, and the second friction layer 3 is made of modified PAN nanofiber film, namely PANA from Example 1. Furthermore, this embodiment provides a flexible wearable triboelectric nanogenerator friction layer material and preparation method based on APTES-modified PAN. By modifying the friction material, the triboelectric charging capability is improved, thereby significantly enhancing the output performance of the triboelectric nanogenerator.

[0064] Example 1: The preparation method of the friction layer material of the flexible wearable triboelectric nanogenerator based on APTES-modified PAN in this example is carried out according to the following steps:

[0065] (1) Preparation of PANA flexible nanofiber film: 0.7 g PAN was dissolved in 5 mL N,N-dimethylformamide and heated to 80°C with magnetic stirring for 180 minutes until completely dissolved. 335 μl APTES was added and stirred for 30 minutes to obtain a pale yellow transparent precursor solution. The prepared precursor solution was poured into a 10 mL syringe and extruded through a metal nozzle at a rate of 1 mL / h. During electrospinning, a voltage of 17 kV was applied, and the distance between the metal nozzle and the receiving plate was maintained at 15 cm. The spun nanofibers were dried in a vacuum drying oven at 105°C for 15 hours until all the solvent evaporated to obtain a PANA flexible nanofiber film.

[0066] (2) Fabrication of flexible triboelectric nanogenerator based on PANA: Copper film, PET film, PANA film and copper film (size 4cm×4cm) are stacked and assembled in sequence to form the flexible triboelectric nanogenerator structure described in Embodiment 7.

[0067] Comparative Example 1: The fabrication method of the PAN-based flexible triboelectric nanogenerator in this comparative example is carried out according to the following steps:

[0068] Similar to Example 1, except that APTES is no longer added in step (1).

[0069] Transmission electron microscopy images of PANA prepared in Example 1 are shown below. Figure 2 As shown, the PANA film prepared by electrospinning has a filamentous nanofiber structure.

[0070] The X-ray diffraction peak patterns of the PANA film prepared in Example 1 and the PAN film prepared in Comparative Example 1 are as follows: Figure 3 As shown, it can be seen that the introduction of APTES did not destroy the original crystalline phase of PAN compared with PAN film.

[0071] The N1s X-ray photoelectron spectral peaks of the PANA thin film prepared in Example 1 and the PAN thin film prepared in Comparative Example 1 are as follows: Figure 4 As shown, the introduction of APTES is confirmed. Figure 4 The two characteristic peaks at 397.9 eV and 398.7 eV are attributed to PAN, while the characteristic peak at 397.5 eV is attributed to the amino group in APTES, confirming the successful introduction of APTES into the PANA composite.

[0072] The X-ray photoelectron spectral peaks of the Si1s of the PANA thin film prepared in Example 1 and the PAN thin film prepared in Comparative Example 1 are as follows: Figure 5 As shown, this further confirms the introduction of APTES. Figure 5The absence of characteristic peaks for Si in PAN, and the presence of a characteristic peak at 100.8 eV, is attributed to the Si-O bonds in APTES, further confirming the successful introduction of APTES into the PANA composite material.

[0073] The voltage output performance of the triboelectric nanogenerators prepared by PANA in Example 1 and PAN in Comparative Example 1 is as follows: Figure 6 As shown, compared with PAN, APTES in PANA can provide more electrons, thereby improving the triboelectric ability and significantly enhancing the output performance of the triboelectric nanogenerator. The output voltage of the modified PANA triboelectric nanogenerator is 404.1V, which is 2.33 times higher than the voltage (173.3V) of the PAN triboelectric nanogenerator.

[0074] The voltage output performance of the PANA-based triboelectric nanogenerator prepared in Example 1 under pressure of 4-16 N, frequency of 1 Hz, contact separation distance of 30 mm, and force-bearing area of ​​4 × 4 cm is as follows: Figure 7 As shown. See also Figure 7 As shown, the voltage output of the triboelectric nanogenerator gradually increases with increasing pressure. However, the voltage output performance of the prepared PANA-based triboelectric nanogenerator does not change significantly with changes in pressure and remains stable, indicating the output stability of the prepared PANA-based triboelectric nanogenerator under different environments.

[0075] The voltage output performance of the PANA-based triboelectric nanogenerator prepared in Example 1 under 16N pressure, 1Hz frequency, 5-30mm contact separation distance, and a force-bearing area of ​​4×4cm is as follows: Figure 8 As shown, the voltage output of the triboelectric nanogenerator gradually increases with the increase of the contact separation distance. The voltage output performance of the prepared PANA-based triboelectric nanogenerator does not change significantly with the change of the contact separation distance and remains stable, indicating the output stability of the prepared PANA-based triboelectric nanogenerator under different environments.

[0076] The voltage output performance of the PANA-based triboelectric nanogenerator prepared in Example 1 under 16N pressure, 1-5Hz frequency, 30mm contact separation distance, and a force-bearing area of ​​4×4cm is as follows: Figure 7 As shown, the voltage output of the triboelectric nanogenerator gradually increases with increasing frequency. Furthermore, the voltage output performance of the prepared PANA-based triboelectric nanogenerator remains stable regardless of frequency changes, demonstrating the output stability of the prepared PANA-based triboelectric nanogenerator under different environments.

[0077] The voltage output performance of the PANA-based triboelectric nanogenerator prepared in Example 1 under 16N pressure, 3Hz frequency, 30mm contact separation distance, and a force-bearing area of ​​4×4cm is as follows: Figure 10 As shown. By Figures 1 to 6 It is known that the PANA-based triboelectric nanogenerator prepared by this invention exhibits excellent stability and can operate under repeated compression and decompression for at least 1 hour and 2 minutes (10,000 cycles) without changing its electromechanical conversion capability.

[0078] Those skilled in the art will understand that the above description is merely a preferred embodiment of the present invention, and the features described in the various embodiments and / or claims of this disclosure can be combined or combined in various ways, even if such combinations or combinations are not explicitly described in this disclosure. This is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

[0079] Although preferred embodiments of the invention have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including both the preferred embodiments and all changes and modifications falling within the scope of the invention. Clearly, those skilled in the art can make various alterations and modifications to the invention without departing from its spirit and scope. Thus, if these modifications and modifications of the invention fall within the scope of the claims and their equivalents, the invention is also intended to include these modifications and modifications.

Claims

1. A method for preparing a flexible wearable friction nanogenerator friction layer material based on APTES modified PAN, characterized in that, The method comprises the following steps: S1, dissolving polyacrylonitrile in N,N-dimethylformamide solution, heating and stirring to obtain a polymer precursor; S2, adding 3-aminopropyl triethoxysilane to the polymer precursor and stirring uniformly to obtain a spinning solution; S3, preparing the spinning solution into a nanofiber film through an electrospinning process; S4, drying the prepared nanofiber film to obtain a friction layer material; The concentration of the polymer in the N,N-dimethylformamide solution in S1 is 5-20wt%. The heating temperature in S1 is 50-90℃.

2. The method for preparing flexible wearable friction nanogenerator friction layer material based on APTES modified PAN according to claim 1, characterized in that, The solvent in the N,N-dimethylformamide solution in S1 is water, ethanol, dimethyl sulfoxide or N-methyl pyrrolidone.

3. A flexible tribo-nanogenerator tribo-layer material based on APTES modified PAN characterized in that, The friction layer material is obtained by the preparation method in any one of claims 1-2.

4. A method for preparing a flexible friction nanogenerator, characterized in that, The flexible friction nanogenerator friction layer material based on APTES modified PAN in claim 3 is used as the second friction layer (3). 5.The method of claim 4, wherein the flexible frictional nanogenerator is prepared by the steps of, The first friction layer (2) is polyethylene terephthalate, thermoplastic polyurethane elastomer, polytetrafluoroethylene or nylon 66. 6.The method of claim 5, wherein the flexible frictional nanogenerator is prepared by the steps of, The material of the first conductive electrode layer (1) and the second conductive electrode layer (4) is gold, silver, aluminum, iron, copper, carbon nanotube, graphene or fullerene. 7.The method of claim 6, wherein the flexible frictional nanogenerator is prepared by, The thickness of the first conductive electrode layer (1) and the second conductive electrode layer (4) is in the range of 60-100μm.

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