Full-leather-based friction nano generator with high sensitivity and preparation method thereof
By internal modification and surface functionalization of the leather, combined with self-assembled single-layer technology, a full-leather-based friction nanogenerator is constructed, which solves the problem of low friction charge transfer efficiency and achieves high sensitivity charge transfer efficiency.
Patent Information
- Application Number
- CN202411366868.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-29
- Publication Date
- 2024-12-27
AI Technical Summary
During use, existing friction nanogenerators have reduced friction charge transfer efficiency and poor sensitivity due to material separation.
By internal modification and surface functionalization of the leather, self-assembled single molecular layers (SAMs) were introduced, hydroxylated treatment was performed using low-temperature plasma technology, and the leather was soaked in different silane hydrolysates to form amyotrogenation and fluorination modifications. The leather is used as a friction positive and negative layer, and is combined with copper wire to construct a full leather-based friction nanogenerator.
It effectively improves the electrical properties of leather, improves the friction charge transfer efficiency, and gives high sensitivity to the full leather-based friction nanogenerator, avoiding the problem of low charge transfer efficiency caused by material separation.
Smart Images
Figure CN119210204A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of friction nanogenerators, and in particular relates to a fully leather-based friction nanogenerator with high sensitivity. The present invention also relates to a method for preparing the fully leather-based friction nanogenerator with high sensitivity. Background Art
[0002] With the rapid development of the Internet of Things and 5G communications, the development of smart wearable devices is changing with each passing day. At present, the commonly used power supply devices for smart wearable electronic devices are traditional rigid batteries, which have limited capacity, poor flexibility and difficulty in degradation, limiting the development of smart wearable electronic devices. Flexible friction nanogenerators (F-TENGs) made of natural products are expected to effectively solve the energy supply problem of smart wearable devices because they can provide green and sustainable energy and are easy to degrade. Leather is a natural material with a multi-level pore structure. The surface of its collagen fibers is rich in active functional groups such as amino and carboxyl groups, which can effectively enhance interfacial interactions and lay the foundation for the construction of functionalized leather. At the same time, leather has good flexibility and durability, and it has great advantages when used as a substrate for wearable electronic products. However, leather itself is weakly electropositive, so it needs to be modified to enhance the electrical polarity of leather in order to realize the efficient application of all-leather-based friction nanogenerators in flexible wearable devices.
[0003] Self-assembled monolayers (SAMs) are ordered films that are spontaneously arranged on the solid surface through the interaction between active molecules. SAMs can design molecular structures with different functions according to needs, providing precise interface control capabilities for triboelectric materials. In addition, the formed molecular layer can evenly cover the material, reduce the interface resistance of the material, and enhance the charge transfer efficiency between materials, thereby improving the sensitivity of the triboelectric nanogenerator. Among them, when the active molecules of the self-assembled monolayer are silane molecules, due to the large atomic radius and 3d empty orbital of Si atoms, it is easier to participate in the transfer and redistribution of electrons during the friction process; O atoms have strong electronegativity and can act as electron receptors to help balance the distribution of triboelectric charges. Therefore, the introduction of Si and O atoms can change the energy level structure of the friction layer surface, making it easier for electrons to migrate and redistribute on the surface, which helps to transfer faster during the friction process. In addition, the strong binding force between SAMs based on silane molecules and the friction layer makes it difficult for the friction layer material to experience performance degradation after multiple cycles. In summary, SAMs based on silane molecules have broad application prospects in the fields of triboelectric sensors and energy harvesting devices. Summary of the invention
[0004] The purpose of the present invention is to provide a fully leather-based friction nanogenerator with high sensitivity, which solves the problem of reduced friction charge transfer efficiency and poor sensitivity caused by material separation during the use of existing friction nanogenerators.
[0005] Another object of the present invention is to provide a method for preparing a fully leather-based friction nanogenerator with high sensitivity.
[0006] The first technical solution adopted by the present invention is: a method for preparing a highly sensitive all-leather-based friction nanogenerator, comprising the following steps:
[0007] Step 1: Prepare two pieces of leather and perform internal modification on each piece;
[0008] Step 2, performing surface amination modification on one part of the internally modified leather, and performing surface fluorination modification on the other part;
[0009] Surface amination modification: Use low-temperature plasma technology to perform surface hydroxylation on the leather, then immerse the leather in 3-aminopropyltriethoxysilane hydrolyzate, clean it with deionized water ultrasonically, and dry it at room temperature;
[0010] Surface fluorination modification: The leather surface is hydroxylated using low-temperature plasma technology, and then the leather is placed in a 1H,1H,2H,2H-perfluorodecyltriethoxysilane hydrolyzate for reaction, and then washed with water and acetone, and then ultrasonically cleaned;
[0011] Step 3: Use the leather with surface amino modification as the positive friction layer and the leather with surface fluorination modification as the negative friction layer, and then attach copper wire to the two leather grains to construct a full leather-based friction nanogenerator.
[0012] The first technical solution of the present invention is also characterized in that:
[0013] The process of internal modification of each leather in step 1 is as follows: 3 mL of polycarboxyl cage silsesquioxane solution and 1 g of leather are added to 50 mL of deionized water, shaken at room temperature for 3 hours, then 0.5 g of pyrrole monomer is added, the temperature is controlled at 0-4°C in an ice water bath, and after stirring for 1 hour, ferric chloride solution is added dropwise. After the addition is completed, the reaction is carried out for 2 hours, and the leather is washed with deionized water 3-5 times and then ultrasonically cleaned for 15 minutes to obtain the internally modified leather.
[0014] The hydroxylation treatment conditions in the surface amination modification of step 2 are as follows: treatment in a low-temperature plasma generator with a power of 100 kW for 5 to 25 minutes, the amount of 3-aminopropyltriethoxysilane hydrolyzate is 10 to 50 g and the concentration is 10 wt %, the immersion time is 12 to 36 hours, and ultrasonic cleaning with deionized water is performed for 5 minutes.
[0015] The hydroxylation treatment conditions in the surface fluorination modification of step 2 are as follows: treatment in a low-temperature plasma generator with a power of 100 kW for 10 min, the amount of 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane hydrolyzate is 10 to 50 g and the concentration is 5 to 25 wt %, the reaction time is 24 h, and it is washed with water and acetone for 3 to 5 times, and ultrasonically cleaned for 5 min.
[0016] The second technical solution adopted by the present invention is: a fully leather-based friction nanogenerator with high sensitivity prepared by a method for preparing a fully leather-based friction nanogenerator with high sensitivity.
[0017] The beneficial effects of the present invention are as follows: the highly sensitive all-leather-based triboelectric nanogenerator and its preparation method of the present invention, through SAMs, the surface functionalization modification of leather is carried out, and siloxanes containing different electron-withdrawing / donating groups are introduced into the leather surface to effectively improve the electrical positive / negative properties of the leather, and LPP-NH2 with good electropositivity and LPP-F with electronegativity are obtained, and LPP-NH2 containing electron-donating groups is used as the triboelectric positive layer, and LPP-F containing electron-withdrawing groups is used as the triboelectric negative layer to construct the all-leather-based triboelectric nanogenerator. In addition, thanks to the natural hierarchical pore structure of leather, the problem of low triboelectric charge transfer efficiency caused by material separation during the use of the triboelectric nanogenerator is effectively avoided, giving the all-leather-based triboelectric nanogenerator excellent sensitivity. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 It is a schematic diagram of the sensitivity performance test of the highly sensitive all-leather-based friction nanogenerator prepared in Example 1 of the present invention. DETAILED DESCRIPTION
[0019] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.
[0020] The present invention provides a method for preparing a highly sensitive all-leather-based friction nanogenerator, comprising the following steps:
[0021] Step 1: Preparation of internally modified leather LPP
[0022] 3 mL of polycarboxyl cage silsesquioxane solution (PCOOH) and 1 g of leather were added to 50 mL of deionized water, respectively, and shaken for 3 h at room temperature, then 0.5 g of pyrrole monomer (Py) was added, the temperature was controlled at 0-4 ° C in an ice water bath, and after stirring for 1 h, ferric chloride solution (FeCl3) was slowly added dropwise, and after the solution was added dropwise, the reaction was continued for 2 h, and after washing with deionized water for 3-5 times, ultrasonic cleaning was performed for 15 min to obtain internally modified leather (LPP);
[0023] Step 2: Preparation of surface modified leather
[0024] (1) Preparation of amino-modified leather
[0025] The leather surface is subjected to hydroxylation treatment by a low-temperature plasma generator, and after being treated for 5 to 25 minutes at a power of 100 kW, a hydroxylated modified leather is obtained; the modified leather material subjected to the hydroxylation treatment is immediately immersed in 10 to 50 g of a 10 wt% 3-aminopropyltriethoxysilane (KH550) hydrolyzate, and after being immersed for 12 to 36 hours, the leather is ultrasonically cleaned with deionized water for 5 minutes, and dried at room temperature to obtain an amino modified leather (LPP-NH2);
[0026] (2) Preparation of fluorinated modified leather
[0027] The leather is subjected to surface hydroxylation treatment by a low-temperature plasma generator, and after treatment for 10 minutes at a power of 100 kW, a hydroxylated modified leather is obtained; the modified leather subjected to the hydroxylation treatment is placed in 10 to 50 g of a 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (PFDTES) hydrolyzate with a concentration of 5 to 25 wt %, and after reacting for 24 hours, the leather is washed with water and acetone for 3 to 5 times, and ultrasonically washed for 5 minutes, to obtain a surface fluorinated modified leather (LPP-F);
[0028] Step 3: Use the LPP-NH2 obtained in step 2 as the tribopositive layer and LPP-F as the tribonegative layer, and use 3M nano glue to attach the copper wire to the modified leather grain surface to construct a full leather-based tribonanogenerator.
[0029] Through the above-mentioned method, the highly sensitive all-leather-based triboelectric nanogenerator and its preparation method of the present invention, by adding PCOOH and PPy inside the leather, realizes the simultaneous improvement of the dielectric constant and conductivity of the leather, and enhances the charge capture and transmission performance of the leather; then the leather is surface functionalized by SAMs, and siloxanes containing different electron-withdrawing / donating groups are introduced into the leather surface to effectively improve the positive / negative properties of the leather, and LPP-NH2 with good positive properties and LPP-F with electronegativity are obtained, and LPP-NH2 containing electron-donating groups is used as the triboelectric positive layer, and LPP-F containing electron-withdrawing groups is used as the triboelectric negative layer to construct a fully leather-based triboelectric nanogenerator. In addition, thanks to the natural hierarchical pore structure of the leather, the grain surface of the leather is used as the electrode layer and the flesh surface is used as the friction layer, which effectively avoids the problem of low triboelectric charge transfer efficiency caused by material separation during the use of the triboelectric nanogenerator, and gives the fully leather-based triboelectric nanogenerator excellent sensitivity.
[0030] Example 1
[0031] Step 1: Add 3 mL of PCOOH and 1 g of leather to 50 mL of deionized water respectively, shake at room temperature for 3 h, then add 0.5 g of Py, control the temperature to 0°C in an ice-water bath, stir and react for 1 h, then slowly add FeCl3, wait for the solution to be added, react for 2 h, wash with deionized water 5 times, and then ultrasonically clean for 15 min to obtain LPP.
[0032] Step 2: Preparation of surface modified leather
[0033] (1) Preparation of amino-modified leather
[0034] The leather surface was subjected to hydroxylation treatment by a low-temperature plasma generator, and after treatment for 10 minutes at a power of 100 kW, a hydroxylated modified leather was obtained; the modified leather material subjected to hydroxylation treatment was immediately immersed in 40 g of a 10 wt% KH550 hydrolyzate, and after immersion for 24 hours, the leather was ultrasonically cleaned with deionized water for 5 minutes, and dried at room temperature to obtain LPP-NH2;
[0035] (2) Preparation of fluorinated modified leather
[0036] The leather was surface hydroxylated by a low-temperature plasma generator at a power of 100 kW for 10 minutes to obtain hydroxylated modified leather. The hydroxylated modified leather was placed in 20 g of 5 wt% PFDTES hydrolyzate and reacted for 24 hours. The leather was then washed with water and acetone for 5 times and ultrasonically cleaned for 5 minutes to obtain LPP-F.
[0037] Step 3: Use the LPP-NH2 obtained in step 2 as the tribopositive layer and LPP-F as the tribonegative layer, and use 3M nano glue to attach the copper wire to the modified leather grain surface to construct a full leather-based tribonanogenerator.
[0038] like Figure 1 As shown, the sensitivity of the friction nanogenerator prepared in Example 1 was tested. It can be seen that the sensitivity can reach 10.89V kPa by linear fitting the output voltage under different pressures. -1 , so it has extremely high sensitivity.
[0039] Example 2
[0040] Step 1: Add 3 mL of PCOOH and 1 g of leather into 50 mL of deionized water respectively, shake at room temperature for 3 h, then add 0.5 g of Py, control the temperature at 2°C in an ice-water bath, stir and react for 1 h, then slowly add FeCl3, wait for the solution to be added, react for 2 h, wash with deionized water 4 times, and then ultrasonically clean for 15 min to obtain LPP.
[0041] Step 2: Preparation of surface modified leather
[0042] (1) Preparation of amino-modified leather
[0043] The leather surface was hydroxylated by a low-temperature plasma generator, and the hydroxylated modified leather was obtained after the treatment at a power of 100 kW for 5 minutes; the modified leather material after the hydroxylation treatment was immediately immersed in 10 g of 10 wt% KH550 hydrolyzate, and after immersion for 12 hours, it was ultrasonically cleaned with deionized water for 5 minutes and dried at room temperature to obtain LPP-NH2;
[0044] (2) Preparation of fluorinated modified leather
[0045] The leather was surface hydroxylated by a low-temperature plasma generator at a power of 100 kW for 10 min to obtain hydroxylated modified leather. The hydroxylated modified leather was placed in 30 g of 10 wt% PFDTES hydrolyzate and reacted for 24 h. The leather was then washed with water and acetone for 3 times and ultrasonically cleaned for 5 min to obtain LPP-F.
[0046] Step 3: Use the LPP-NH2 obtained in step 2 as the tribopositive layer and LPP-F as the tribonegative layer, and use 3M nano glue to attach the copper wire to the modified leather grain surface to construct a full leather-based tribonanogenerator.
[0047] Example 3
[0048] Step 1: Add 3 mL of PCOOH and 1 g of leather to 50 mL of deionized water respectively, shake at room temperature for 3 h, then add 0.5 g of Py, control the temperature to 4 ° C in an ice-water bath, stir and react for 1 h, then slowly add FeCl3, wait for the solution to be added, react for 2 h, wash with deionized water 3 times, and then ultrasonically clean for 15 min to obtain LPP.
[0049] Step 2: Preparation of surface modified leather
[0050] (1) Preparation of amino-modified leather
[0051] The leather surface was subjected to hydroxylation treatment by a low-temperature plasma generator, and after treatment for 25 minutes at a power of 100 kW, a hydroxylated modified leather was obtained; the modified leather material subjected to hydroxylation treatment was immediately immersed in 50 g of a 10 wt% KH550 hydrolyzate, and after immersion for 36 hours, the leather was ultrasonically cleaned with deionized water for 5 minutes, and dried at room temperature to obtain LPP-NH2;
[0052] (2) Preparation of fluorinated modified leather
[0053] The leather was surface hydroxylated by a low-temperature plasma generator at a power of 100 kW for 10 minutes to obtain hydroxylated modified leather. The hydroxylated modified leather was placed in 50 g of 25 wt% PFDTES hydrolyzate and reacted for 24 hours. The leather was then washed with water and acetone for 4 times and ultrasonically cleaned for 5 minutes to obtain LPP-F.
[0054] Step 3: Use the LPP-NH2 obtained in step 2 as the tribopositive layer and LPP-F as the tribonegative layer, and use 3M nano glue to attach the copper wire to the modified leather grain surface to construct a full leather-based tribonanogenerator.
[0055] Example 4
[0056] Step 1: Add 3 mL of PCOOH and 1 g of leather to 50 mL of deionized water respectively, shake at room temperature for 3 h, then add 0.5 g of Py, control the temperature to 0°C in an ice-water bath, stir and react for 1 h, then slowly add FeCl3, wait for the solution to be added, react for 2 h, wash with deionized water 5 times, and then ultrasonically clean for 15 min to obtain LPP.
[0057] Step 2: Preparation of surface modified leather
[0058] (1) Preparation of amino-modified leather
[0059] The leather surface was subjected to hydroxylation treatment by a low-temperature plasma generator, and after treatment for 10 minutes at a power of 100 kW, a hydroxylated modified leather was obtained; the modified leather material subjected to hydroxylation treatment was immediately immersed in 30 g of a 10 wt% KH550 hydrolyzate, and after immersion for 36 hours, the leather was ultrasonically cleaned with deionized water for 5 minutes, and dried at room temperature to obtain LPP-NH2;
[0060] (2) Preparation of fluorinated modified leather
[0061] The leather was surface hydroxylated by a low-temperature plasma generator at a power of 100 kW for 10 min to obtain hydroxylated modified leather. The hydroxylated modified leather was placed in 10 g of 10 wt% PFDTES hydrolyzate and reacted for 24 h. The leather was then washed with water and acetone for 3 times and ultrasonically cleaned for 5 min to obtain LPP-F.
[0062] Step 3: Use the LPP-NH2 obtained in step 2 as the tribopositive layer and LPP-F as the tribonegative layer, and use 3M nano glue to attach the copper wire to the modified leather grain surface to construct a full leather-based tribonanogenerator.
[0063] Example 5
[0064] Step 1: Add 3 mL of PCOOH and 1 g of leather into 50 mL of deionized water respectively, shake at room temperature for 3 h, then add 0.5 g of Py, control the temperature to 1°C in an ice-water bath, stir and react for 1 h, then slowly add FeCl3, wait for the solution to be added, react for 2 h, wash with deionized water 5 times, and then ultrasonically clean for 15 min to obtain LPP.
[0065] Step 2: Preparation of surface modified leather
[0066] (1) Preparation of amino-modified leather
[0067] The leather surface was hydroxylated by a low-temperature plasma generator, and the hydroxylated modified leather was obtained after the treatment at a power of 100 kW for 10 minutes; the modified leather material after the hydroxylation treatment was immediately immersed in 30 g of 10 wt% KH550 hydrolyzate, and after immersion for 30 hours, it was ultrasonically cleaned with deionized water for 5 minutes and dried at room temperature to obtain LPP-NH2;
[0068] (2) Preparation of fluorinated modified leather
[0069] The leather was surface hydroxylated by a low-temperature plasma generator at a power of 100 kW for 10 min to obtain hydroxylated modified leather. The hydroxylated modified leather was placed in 40 g of 10 wt% PFDTES hydrolyzate and reacted for 24 h. The leather was then washed with water and acetone for 5 times and ultrasonically cleaned for 5 min to obtain LPP-F.
[0070] Step 3: Use the LPP-NH2 obtained in step 2 as the tribopositive layer and LPP-F as the tribonegative layer, and use 3M nano glue to attach the copper wire to the modified leather grain surface to construct a full leather-based tribonanogenerator.
Claims
1. A method for preparing a highly sensitive all-leather-based friction nanogenerator, characterized in that: The following steps are involved: Step 1: Prepare two pieces of leather and perform internal modification on each piece; Step 2, performing surface amination modification on one portion of the internally modified leather, and performing surface fluorination modification on the other portion; Surface amination modification: Use low-temperature plasma technology to perform surface hydroxylation on the leather, then immerse the leather in 3-aminopropyltriethoxysilane hydrolyzate, clean it with deionized water ultrasonically, and dry it at room temperature; Surface fluorination modification: The leather surface is hydroxylated using low-temperature plasma technology, and then the leather is placed in a 1H,1H,2H,2H-perfluorodecyltriethoxysilane hydrolyzate for reaction, and then washed with water and acetone, and then ultrasonically cleaned; Step 3: Use the leather with surface amino modification as the positive friction layer and the leather with surface fluorination modification as the negative friction layer, and then attach copper wire to the two leather grains to construct a full leather-based friction nanogenerator.
2. The method for preparing a highly sensitive all-leather-based friction nanogenerator according to claim 1, characterized in that: The process of internal modification of each leather in step 1 is as follows: 3 mL of polycarboxyl cage silsesquioxane solution and 1 g of leather are added to 50 mL of deionized water, shaken at room temperature for 3 hours, then 0.5 g of pyrrole monomer is added, the temperature is controlled at 0-4°C in an ice-water bath, stirred for reaction for 1 hour, and then ferric chloride solution is added dropwise. After the addition is completed, the reaction is carried out for 2 hours, and the leather is washed with deionized water for 3-5 times and then ultrasonically cleaned for 15 minutes to obtain the leather after internal modification.
3. The method for preparing a highly sensitive all-leather-based friction nanogenerator according to claim 1, characterized in that: The hydroxylation treatment conditions in the surface amination modification of step 2 are as follows: treatment in a low-temperature plasma generator with a power of 100 kW for 5 to 25 minutes, the amount of 3-aminopropyltriethoxysilane hydrolyzate is 10 to 50 g and the concentration is 10 wt %, the immersion time is 12 to 36 hours, and ultrasonic cleaning with deionized water is performed for 5 minutes.
4. The method for preparing a highly sensitive all-leather-based friction nanogenerator according to claim 1, characterized in that: The hydroxylation treatment conditions in the surface fluorination modification of step 2 are as follows: treating in a low-temperature plasma generator with a power of 100 kW for 10 minutes, using 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane hydrolyzate in an amount of 10 to 50 g and a concentration of 5 to 25 wt%, reacting for 24 hours, washing with water and acetone for 3 to 5 times, and ultrasonically cleaning for 5 minutes.
5. The all-leather-based friction nanogenerator with high sensitivity prepared by the preparation method of the all-leather-based friction nanogenerator with high sensitivity as claimed in claim 1.