A high-elastic sbs-tea powder friction layer, a preparation method thereof and application thereof in a friction nanogenerator

Abstract

The application relates to a high-elastic SBS-tea powder friction layer, a preparation method thereof and application in a friction nanogenerator. The application belongs to the technical field of friction nanogeneration. The application aims to solve the technical problem that the elasticity and power generation performance of an existing high-molecular polymer-based friction layer are not high. The application adopts hydroxylated SBS and tea powder as raw materials to prepare an SBS-tea powder film for a friction nanogenerator. The waste tea powder increases the number of H atoms in the friction layer, provides more electrons for the high-electronegativity F atoms of PTFE, and therefore increases the electric output characteristics of the friction nanogenerator, greatly improves the power generation effect, and provides theoretical support for the application of the TENG in a vehicle-road coupled intelligent traffic monitoring system.

Description

Technical Field

[0001] This invention belongs to the field of triboelectric nanogenerator technology, specifically relating to a highly elastic SBS-tea powder friction layer, its preparation method, and its application in triboelectric nanogenerators. Background Technology

[0002] In the transportation industry, achieving sustainable monitoring of transportation systems and utilizing clean energy as a power source has always been one of the core challenges that urgently needs to be addressed. In recent years, significant progress has been made in the research and development of intelligent traffic monitoring and sensing systems. These systems widely integrate various technologies such as ultrasonic, infrared, and acoustic sensors, and are effectively applied in several key areas, including vehicle queue length estimation, driver status monitoring, early detection of vehicle mechanical defects, traffic flow data collection, road condition assessment, bridge vibration and displacement monitoring, and traffic vehicle tracking. However, these sensors generally rely on external power supplies, and traditional batteries have limitations such as limited lifespan, inconvenient and rigid casings, and significant environmental impact, severely restricting long-term and continuous monitoring operations.

[0003] Given the aforementioned limitations, exploring and applying clean energy to support the long-term monitoring of intelligent transportation systems is particularly important and urgent. Triboelectric nanogenerators (TENGs), as an innovative energy harvesting device, can collect mechanical energy from road traffic and vehicle vibrations and convert it into electrical energy, providing a potential energy solution for intelligent traffic monitoring and sensing systems.

[0004] However, in the research and development of TENGs, how to effectively control the surface charge density to manufacture devices with excellent triboelectric properties has become one of the most critical and urgent technical challenges. Linear polymers containing fluorine atoms with high electron affinity, such as polytetrafluoroethylene (PTFE), have been widely used as negative triboelectric layer materials for TENGs, but the lack of elasticity of this material limits the application potential of TENGs in long-term energy harvesting and monitoring. Summary of the Invention

[0005] The purpose of this invention is to solve the technical problems of low elasticity and low power generation performance of existing polymer-based friction layers, and to provide a high-elasticity SBS-tea powder friction layer, its preparation method, and its application in triboelectric nanogenerators.

[0006] One objective of this invention is to provide a method for preparing a high-elastic SBS-tea powder friction layer, the method comprising the following steps:

[0007] Step 1: Dissolve linear SBS in chloroform, then add hydrogen peroxide and formic acid to carry out a hydroxylation reaction. After the reaction is completed, add petroleum ether to the resulting emulsion to precipitate the polymer. Purify, vacuum dry, and grind to obtain hydroxylated SBS.

[0008] Step 2: Dry and grind the waste tea leaves after brewing to obtain tea powder. Then, add the tea powder, silane coupling agent, and nano-silica (SiO2) to a tetrahydrofuran (THF) solution of hydroxylated SBS. Stir magnetically for a certain time at a certain temperature to obtain an SBS-tea powder composite solution. Then, place the solution in a mold and defoam under vacuum conditions and solidify it into a thin film to obtain a high-elastic SBS-tea powder friction layer.

[0009] Further specifying, the mass ratio of linear SBS to chloroform in step 1 is 1:(5-15).

[0010] Further specifying, in step 1, the mass ratio of hydrogen peroxide to formic acid and chloroform is (0.5-1.5):10:10.

[0011] Further specifying, the hydroxylation reaction temperature in step 1 is 50-70℃, and the time is 20-24h.

[0012] Further specifying, the vacuum drying temperature in step 1 is 30-50℃, and the drying time is 20-24h.

[0013] Further specified, the content of hydroxylated SBS in the SBS-tea powder composite solution in step 2 is 10-25wt%, the mass ratio of nano-SiO2 and tea powder to hydroxylated SBS is (10-20):(10-20):100, and the mass ratio of silane coupling agent to nano-SiO2 is (10-20):100.

[0014] Further specifying, the silane coupling agent in step 2 includes 3-thiopropylmethoxysilane.

[0015] Further specifying, in step 2, the mixture is magnetically stirred at 400-600 rpm for 3-6 hours at 50-70℃.

[0016] Further specifying, the curing temperature in step 2 is 60-80℃, and the time is 12-24h.

[0017] The second objective of this invention is to provide a highly elastic SBS-tea powder friction layer obtained by the above method.

[0018] The third objective of this invention is to provide a triboelectric nanogenerator, wherein the negative electrode of the triboelectric nanogenerator comprises the aforementioned highly elastic SBS-tea powder friction layer, and the positive electrode comprises a polytetrafluoroethylene (PTFE) film.

[0019] The fourth objective of this invention is to provide a method for preparing a triboelectric nanogenerator, the method comprising the following steps:

[0020] S1. The above-mentioned high-elastic SBS-tea powder friction layer film is attached to the copper electrode, and then the other side of the copper electrode is attached to the acrylic plate to prepare a negative electrode.

[0021] S2: A polytetrafluoroethylene (PTFE) film is attached to a copper electrode, and then the other side of the copper electrode is attached to an acrylic plate to prepare a positive electrode;

[0022] S3: Connect the four corners of the two acrylic plates with springs to obtain an SBS-tea powder / PTFE triboelectric nanogenerator.

[0023] The fifth objective of this invention is to provide an application of a triboelectric nanogenerator in a vehicle-road coupled intelligent traffic monitoring system.

[0024] The significant advantages of this invention compared to existing technologies are:

[0025] This invention uses hydroxylated SBS and tea powder as raw materials to prepare SBS-tea powder thin films for triboelectric nanogenerators. The waste tea powder increases the number of H atoms in the triboelectric layer, providing more electrons for the highly electronegative F atoms of PTFE. This increases the electrical output characteristics of the triboelectric nanogenerator, significantly improving the power generation effect and providing theoretical support for the application of TENG in vehicle-road coupled intelligent traffic monitoring systems. Attached Figure Description

[0026] Figure 1 A schematic diagram of a triboelectric nanogenerator configuration;

[0027] Figure 2 for Figure 1 Schematic diagram of the structure of the positive and negative friction layers;

[0028] Figure 3 This is a schematic diagram of the connection of the triboelectric nanogenerator testing system;

[0029] Figure 4 for Figure 3 Schematic diagram of the structure of the motion module;

[0030] In the attached diagram, the components represented by each number are as follows:

[0031] 1-Acrylic plate A, 2-Conductive copper electrode A, 3-Negative friction layer, 4-Acrylic plate B, 5-Conductive copper electrode B, 6-Positive friction layer, 7-Support spring, 8-Base plate, 9-Integrated drive and control stepper motor, 10-Motion module, 11-Motor, 12-Stator, 13-Power supply, 14-Computer, 15-Acquisition module, 16-Electrometer, 17-Motion module. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0033] Unless otherwise specified, the experimental methods used in the following examples are conventional methods. The materials, reagents, methods, and instruments used, unless otherwise specified, are all conventional materials, reagents, methods, and instruments in the art, and can be obtained commercially by those skilled in the art.

[0034] The terms “comprising,” “including,” “having,” “containing,” or any other variations thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such a composition, step, method, article, or apparatus.

[0035] In this invention, "an embodiment" or "embodiment" refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that excludes other embodiments.

[0036] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0037] Example 1: The preparation method of the high-elastic SBS-tea powder friction layer in this example is carried out according to the following steps:

[0038] Step 1: In a three-necked flask equipped with a condenser, mechanical stirrer, and thermometer, add 25g of linear SBS (Liaoning Northern Dynasol Synthetic Rubber Co., Ltd., Dynasol 501h, PB ratio 7:3) powder and 250g of chloroform. Start stirring and heat to 50℃ to completely dissolve the SBS. Then add 25g of hydrogen peroxide and 250g of formic acid solution to the flask and react continuously at 60℃ for 24h. After the reaction is complete, cool down and discharge the product. Pour the obtained polymer emulsion into a beaker and add 250g of petroleum ether to precipitate the polymer from the mixed solvent. Repeat the precipitation operation 3 times to purify the product. Place the obtained polymer sample in a vacuum drying oven and vacuum dry at 40℃ for 24h. Grind to a fineness of 200 mesh or higher to obtain hydroxylated SBS powder.

[0039] Step 2: Collect the brewed waste green tea leaves (Huangshan Maofeng), add water and continue soaking for 24 hours. After soaking, place them in an oven to dry at 70℃ for 24 hours. After drying, grind them to 500 mesh to obtain green tea powder.

[0040] Weigh 25g of hydroxylated SBS powder, dissolve it in 67g of THF solution, stir well, and then place the mixture in a magnetic stirrer at 60℃ and 500rpm for 6h to obtain a THF solution of hydroxylated SBS.

[0041] 0.5 g of 3-thiopropylmethoxysilane, 2.5 g of nano-SiO2, and 5 g of green tea powder were added to an SBS / THF solution. The solution was then magnetically stirred at 500 rpm for 5 hours at 60°C to obtain an SBS-green tea powder composite solution. Finally, the SBS-green tea powder composite solution was placed in a 3D-printed mold, placed in a vacuum oven to remove air bubbles, and cured at 70°C for 24 hours to obtain a 100 μm thick SBS-tea powder film. Figure 2 (As shown).

[0042] Application Example 1: Combining Figure 1 The preparation method of the triboelectric nanogenerator includes the following steps:

[0043] First, the SBS-tea powder film and PTFE film of Example 1 were cut into 2cm*2cm pieces;

[0044] Next, the SBS-tea powder film is attached to the conductive copper electrode, and then the other side of the copper electrode is attached to the acrylic plate to prepare a negative electrode.

[0045] Then, the PTFE film is attached to the conductive copper electrode, and the other side of the copper electrode is attached to the acrylic plate to prepare the positive electrode;

[0046] Finally, the two acrylic plates were connected at the four corners with springs to obtain an SBS-tea powder / PTFE triboelectric nanogenerator.

[0047] Combination Figure 3-4 A self-built triboelectric nanogenerator testing system was used to test the triboelectric nanogenerator. During testing, the positive electrode was attached to the vertical plate of the stator 12 in the motion module 17, and the negative electrode was attached to the vertical plate of the mover 11 in the motion module 17. A Keithley 6517B electrometer 16, motion module 17, and acquisition module 15 were controlled, and a high-speed signal acquisition card was used to sample the current and voltage signals obtained during the test at high frequency. The maximum open-circuit voltage of Example 1 was measured; at 10Hz, the maximum open-circuit voltage of Example 1 was 189V.

[0048] Example 2: The preparation method of the high-elastic SBS-tea powder friction layer in this example is carried out according to the following steps:

[0049] Step 1: In a three-necked flask equipped with a condenser, mechanical stirrer, and thermometer, add 25g of linear SBS (Liaoning Northern Dynasol Synthetic Rubber Co., Ltd., Dynasol 501h, PB ratio 7:3) and 250g of chloroform. Start stirring and heat to 50℃ to completely dissolve the SBS. Then add 25g of hydrogen peroxide and 250g of formic acid solution to the flask and react continuously at 60℃ for 24h. After the reaction is complete, cool down and discharge the product. Pour the obtained polymer emulsion into a beaker and add 250g of petroleum ether to precipitate the polymer from the mixed solvent. Repeat the precipitation operation 3 times to purify the product. Place the obtained polymer sample in a vacuum drying oven and vacuum dry at 40℃ for 24h. Grind to a fineness of 200 mesh or higher to obtain hydroxylated SBS powder.

[0050] Step 2: Collect the brewed waste green tea leaves (Huangshan Maofeng), add water and continue soaking for 24 hours. After soaking, place them in an oven to dry at 70℃ for 24 hours. After drying, grind them to 500 mesh to obtain green tea powder.

[0051] Weigh 25g of hydroxylated SBS powder and dissolve it in 68.25g of THF solution. Stir well and place the mixture in a magnetic stirrer at 60℃ and 500rpm for 6h to obtain a THF solution of hydroxylated SBS.

[0052] 0.5 g of 3-thiopropylmethoxysilane, 2.5 g of nano-SiO2, and 3.75 g of green tea powder were added to an SBS / THF solution. The solution was then magnetically stirred at 500 rpm for 5 hours at 60°C to obtain an SBS-green tea powder composite solution. Finally, the SBS-green tea powder composite solution was placed in a 3D-printed mold, placed in a vacuum oven to remove air bubbles, and cured at 70°C for 24 hours to obtain a 100 μm thick SBS-tea powder film. Figure 2 (As shown).

[0053] Application Example 2: Combining Figure 1 The preparation method of the triboelectric nanogenerator includes the following steps:

[0054] First, the SBS-tea powder film and PTFE film from Example 2 were cut into 2cm*2cm pieces;

[0055] Next, the SBS-tea powder film is attached to the conductive copper electrode, and then the other side of the copper electrode is attached to the acrylic plate to prepare a negative electrode.

[0056] Then, the PTFE film is attached to the conductive copper electrode, and the other side of the copper electrode is attached to the acrylic plate to prepare the positive electrode;

[0057] Finally, the two acrylic plates were connected at the four corners with springs to obtain an SBS-tea powder / PTFE triboelectric nanogenerator.

[0058] The electrical output performance was tested using the same method as in Application Example 1. The maximum open-circuit voltage of Example 2 was measured; at 10Hz, the maximum open-circuit voltage of Example 2 was 170V.

[0059] Example 3: The preparation method of the high-elastic SBS-tea powder friction layer in this example is carried out according to the following steps:

[0060] Step 1: In a three-necked flask equipped with a condenser, mechanical stirrer, and thermometer, add 25g of linear SBS (Liaoning Northern Dynasol Synthetic Rubber Co., Ltd., Dynasol 501h, PB ratio 7:3) and 250g of chloroform. Start stirring and heat to 50℃ to completely dissolve the SBS. Then add 25g of hydrogen peroxide and 250g of formic acid solution to the flask and react continuously at 60℃ for 24h. After the reaction is complete, cool down and discharge the product. Pour the obtained polymer emulsion into a beaker and add 250g of petroleum ether to precipitate the polymer from the mixed solvent. Repeat the precipitation operation 3 times to purify the product. Place the obtained polymer sample in a vacuum drying oven and vacuum dry at 40℃ for 24h. Grind to a fineness of 200 mesh or higher to obtain hydroxylated SBS powder.

[0061] Step 2: Collect the brewed waste green tea leaves (Huangshan Maofeng), add water and continue soaking for 24 hours. After soaking, place them in an oven to dry at 70℃ for 24 hours. After drying, grind them to 500 mesh to obtain green tea powder.

[0062] Weigh 25g of hydroxylated SBS powder, dissolve it in 69.5g of THF solution, stir well, and then place the mixture in a magnetic stirrer and stir magnetically at 500rpm for 6h at 60℃ to obtain a THF solution of hydroxylated SBS.

[0063] 0.5 g of 3-thiopropylmethoxysilane, 2.5 g of nano-SiO2, and 2.5 g of green tea powder were added to an SBS / THF solution. The solution was then magnetically stirred at 500 rpm for 5 hours at 60°C to obtain an SBS-green tea powder composite solution. Finally, the SBS-green tea powder composite solution was placed in a 3D-printed mold, placed in a vacuum oven to remove air bubbles, and cured at 70°C for 24 hours to obtain a 100 μm thick SBS-tea powder film. Figure 2 (As shown).

[0064] Application Example 3: Combining Figure 1 The preparation method of the triboelectric nanogenerator includes the following steps:

[0065] First, the SBS-tea powder film and PTFE film of Example 3 were cut into 2cm*2cm pieces;

[0066] Next, the SBS-tea powder film is attached to the conductive copper electrode, and then the other side of the copper electrode is attached to the acrylic plate to prepare a negative electrode.

[0067] Then, the PTFE film is attached to the conductive copper electrode, and the other side of the copper electrode is attached to the acrylic plate to prepare the positive electrode;

[0068] Finally, the two acrylic plates were connected at the four corners with springs to obtain an SBS-tea powder / PTFE triboelectric nanogenerator.

[0069] The electrical output performance was tested using the same method as in Application Example 1. The maximum open-circuit voltage of Example 3 was measured; at 10Hz, the maximum open-circuit voltage of Example 3 was 155V.

[0070] Comparative Example 1: The preparation method of the SBS film in this embodiment is carried out according to the following steps:

[0071] Step 1: In a three-necked flask equipped with a condenser, mechanical stirrer, and thermometer, add 25g of linear SBS (Liaoning Northern Dynasol Synthetic Rubber Co., Ltd., Dynasol 501h, PB ratio 7:3) and 250g of chloroform. Start stirring and heat to 50℃ to completely dissolve the SBS. Then add 25g of hydrogen peroxide and 250g of formic acid solution to the flask and react continuously at 60℃ for 24h. After the reaction is complete, cool down and discharge the product. Pour the obtained polymer emulsion into a beaker and add 250g of petroleum ether to precipitate the polymer from the mixed solvent. Repeat the precipitation operation 3 times to purify the product. Place the obtained polymer sample in a vacuum drying oven and vacuum dry at 40℃ for 24h. Grind to a fineness of 200 mesh or higher to obtain hydroxylated SBS powder.

[0072] Step 2: Weigh 25g of hydroxylated SBS powder and dissolve it in 72g of THF solution. Stir until homogeneous, then place the mixture in a magnetic stirrer at 60℃ and 500rpm for 6 hours to obtain a THF solution of hydroxylated SBS. Add 0.5g of 3-thiopropylmethoxysilane and 2.5g of nano-SiO2 to the SBS / THF solution, and continue stirring in a magnetic stirrer at 60℃ and 500rpm for 5 hours to obtain an SBS solution. Finally, place the SBS solution in a 3D-printed mold, place it in a vacuum oven to remove air bubbles, and cure at 70℃ for 24 hours to obtain a 100μm thick SBS film. (e.g.) Figure 2 (As shown).

[0073] Comparative application example 1: Combining Figure 1 The preparation method of the triboelectric nanogenerator includes the following steps:

[0074] First, the SBS film and PTFE film of Comparative Example 1 were cut into 2cm*2cm pieces;

[0075] Next, the SBS film is attached to the conductive copper electrode, and then the other side of the copper electrode is attached to the acrylic plate to prepare a negative electrode.

[0076] Then, the PTFE film is attached to the conductive copper electrode, and the other side of the copper electrode is attached to the acrylic plate to prepare the positive electrode;

[0077] Finally, the two acrylic plates were connected at the four corners with springs to obtain an SBS / PTFE triboelectric nanogenerator.

[0078] The electrical output performance test method is the same as that in Application Example 1. The maximum open-circuit voltage of Comparative Example 1 was measured. At 10Hz, the maximum open-circuit voltage of Comparative Example 1 was 120V.

[0079] The SBS-tea powder / PTFE triboelectric nanogenerator developed in this invention has a higher open-circuit voltage because the chemical components in the waste tea powder can enhance the charge transfer between the SBS-tea powder film and the PTFE triboelectric layer. The waste tea powder increases the number of H atoms in the triboelectric layer, providing more electrons for the highly electronegative F atoms of PTFE, thus increasing the electrical output characteristics of the triboelectric nanogenerator.

[0080] The above description is merely a preferred embodiment of the present invention. These specific embodiments are different implementations based on the overall concept of the present invention, and the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing a high-elastic SBS-tea powder friction layer, characterized in that, The method described: Step 1: Dissolve linear SBS in chloroform, then add hydrogen peroxide and formic acid to carry out a hydroxylation reaction. After the reaction is completed, add petroleum ether to the resulting emulsion to precipitate the polymer. Purify, vacuum dry, and grind to obtain hydroxylated SBS. Step 2: Dry and grind the waste tea leaves after brewing to obtain tea powder. Then, add the tea powder, silane coupling agent, and nano-SiO2 to a THF solution of hydroxylated SBS. Stir magnetically for a certain time at a certain temperature to obtain an SBS-tea powder composite solution. Then, place the solution in a mold and defoam under vacuum conditions to solidify it into a thin film to obtain a high-elastic SBS-tea powder friction layer. The mass ratio of nano-SiO2 and tea powder to hydroxylated SBS is (10-20):(10-20):

100.

2. The method according to claim 1, characterized in that, In step 1, the mass ratio of linear SBS to chloroform is 1:(5-15), and the mass ratio of hydrogen peroxide to formic acid and chloroform is (0.5-1.5):10:

10.

3. The method according to claim 1, characterized in that, In step 1, the hydroxylation reaction is carried out at a temperature of 50-70℃ for 20-24 hours.

4. The method according to claim 1, characterized in that, In step 2, the content of hydroxylated SBS in the SBS-tea powder composite solution is 10-25 wt%, and the mass ratio of silane coupling agent to nano-SiO2 is (10-20):

100.

5. The method according to claim 1, characterized in that, Silane coupling agents include 3-thiopropylmethoxysilane.

6. The method according to claim 1, characterized in that, In step 2, the mixture is magnetically stirred at 400-600 rpm at 50-70℃ for 3-6 hours, and the curing temperature is 60-80℃ for 12-24 hours.

7. The high-elastic SBS-tea powder friction layer obtained by the method according to any one of claims 1-6.

8. A triboelectric nanogenerator, characterized in that, The negative electrode of the triboelectric nanogenerator comprises the high-elastic SBS-tea powder friction layer as described in claim 7, and the positive electrode comprises a PTFE film.

9. The method for preparing the triboelectric nanogenerator according to claim 8, characterized in that, The method steps are as follows: S1. A high-elastic SBS-tea powder friction layer film is attached to a copper electrode, and then the other side of the copper electrode is attached to an acrylic plate to prepare a negative electrode. S2: PTFE film is attached to copper electrode, and then the other side of copper electrode is attached to acrylic plate to prepare positive electrode; S3: Connect the four corners of the two acrylic plates with springs to obtain an SBS-tea powder / PTFE triboelectric nanogenerator.

10. The application of the triboelectric nanogenerator as described in claim 8 in a vehicle-road coupled intelligent traffic monitoring system.

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