Flame-retardant leather-based triboelectricity self-energized sensor and preparation method thereof

Abstract

The invention discloses a flame-retardant leather-based triboelectric self-energized sensor and a preparation method thereof, and the method specifically comprises the steps: taking leather as a flexible substrate, adopting a leather-making wet processing technology, and selecting octa-amino cage type silsesquioxane (NPOSS) to modify leather collagen fibers to obtain NPOSS modified leather (NPOSS / leather); and constructing the flame-retardant leather-based triboelectricity self-energized sensor by taking a polytetrafluoroethylene film as a triboelectricity negative layer and copper as an electrode layer. The limit oxygen index (LOI) value of the prepared NPOSS / leather triboelectric positive layer material is 29.2%, a sensor shows high stability in a 160 DEG C high-temperature environment, and the output retention rate reaches 88%. The sensor can be used as a self-powered sensor for collecting biological energy in a high-temperature environment, and is of great significance to motion sensing and fire scene evacuation rescue in the high-temperature environment.

Description

Technical Field

[0001] The present invention belongs to the technical field of sensor preparation, and in particular relates to a flame-retardant leather-based triboelectric self-powered sensor, and also relates to a preparation method of the flame-retardant leather-based triboelectric self-powered sensor. Background Art

[0002] Triboelectric nanogenerators (TENGs) can convert distributed high-entropy energy in the environment into electrical energy. As self-powered micro-nano energy sources and self-driven sensors, they have received widespread attention in the field of flexible / wearable electronic products. Leather, as a natural polymer material, has advantages such as renewability, comfort and biodegradability, which is very consistent with the requirements for substrate materials in the field of flexible smart wearables. Flexible friction nanogenerators based on leather have been reported. However, leather is flammable under open flames and has poor stability in high temperature environments, which seriously limits the application of leather-based friction nanogenerators in high temperature and fire scenarios. Therefore, it is of great significance to improve the flame retardancy and stability of leather-based friction nanogenerators in high temperature environments. Summary of the invention

[0003] The first objective of the present invention is to provide a flame-retardant leather-based friction electric self-powered sensor to solve the problem that the leather-based friction self-powered flexible sensor is flammable and has poor stability in high temperature environments.

[0004] To achieve the above purpose, the technical solution adopted by the present invention is: a flame-retardant leather-based triboelectric self-powered sensor is constructed by using octaamino cage silsesquioxane modified leather as a tribopositive layer, PTFE film as a tribone negative layer, and copper as an electrode layer; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0005] The second object of the present invention is to provide a method for preparing a flame-retardant leather-based friction electric self-powered sensor to solve the problem that the leather-based friction self-powered flexible sensor is flammable and has poor stability in high temperature environments.

[0006] To achieve the above purpose, the technical solution adopted by the present invention is: a method for preparing a flame-retardant leather-based triboelectric self-powered sensor, which is specifically implemented according to the following steps: Step 1: immerse the leather in a salt solution, adjust the pH to 4.5, add octaamino cage silsesquioxane and shake, and after shaking, use a formic acid solution to slowly adjust the pH to 3.0, shake again, then wash with water and dry to obtain octaamino cage silsesquioxane modified leather; the mass ratio of leather to octaamino cage silsesquioxane is 1:0.8-4, and the mass ratio of leather to salt solution is: 1:2-2.5; Step 2: Using octaamino cage silsesquioxane modified leather as the triboelectric positive layer, PTFE film as the triboelectric negative layer, and copper as the electrode layer, a flame-retardant leather-based triboelectric self-powered sensor was constructed; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0007] The technical solution of the present invention also has the following characteristics: In step 1, octaamino cage silsesquioxane is added and the shaking time is 1 h to 2 h.

[0008] In step 1, the shaking time is 1 h. In step 1, water washing is performed the next day.

[0009] In step 1, the drying is natural drying.

[0010] In step 1, shake again and let stand overnight.

[0011] In step 1, the salt solution is a sodium chloride solution with a mass concentration of 6 wt%-8 wt%.

[0012] The beneficial effects of the present invention are as follows: the preparation method of the flame-retardant leather-based triboelectric self-powered sensor of the present invention utilizes the advantages of leather such as good flexibility and biodegradability, introduces octaamino cage silsesquioxane into leather through leather wet processing technology, imparts flame retardancy to the leather, and enhances its electron supply capacity, improves triboelectric sensing performance, uses the modified leather as a tribopositive layer, and polytetrafluoroethylene film as a tribopositive layer to construct a flame-retardant leather-based triboelectric self-powered sensor. The limiting oxygen index (LOI) value of the prepared octaamino cage silsesquioxane modified leather triboelectric positive layer material is 29.2%, and the sensor exhibits high stability in a high temperature environment of 160°C, with an output retention rate of 88%. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 It is a structural schematic diagram of a leather-based triboelectric self-powered sensor obtained by a method for preparing a flame-retardant leather-based triboelectric self-powered sensor of the present invention.

[0014] Figure 2 The invention discloses output performance of a flame-retardant leather-based triboelectric self-powered sensor at different temperatures obtained by the method for preparing the flame-retardant leather-based triboelectric self-powered sensor. DETAILED DESCRIPTION

[0015] The technical solution of the present invention is further described in detail below in conjunction with the accompanying drawings and specific embodiments.

[0016] Octaamino cage silsesquioxane (NPOSS) is a class of organic-inorganic hybrid materials with a highly symmetrical nanoscale cubic cage skeleton that can maintain its initial physical properties over a wide temperature range and has good flame retardant properties; in addition, the periphery contains abundant electron-donating groups -NH2.

[0017] The present invention proposes to use leather with advantages such as good flexibility and biodegradability as a sensing material, select octaamino cage silsesquioxane to modify leather collagen fibers, and utilize the -NH2 group on the octaamino cage silsesquioxane to enhance the electron-donating capacity of the leather, thereby improving its triboelectric sensing performance; utilize the Si-O-Si rigid cage structure of the octaamino cage silsesquioxane to impart flame retardancy to the leather, thereby obtaining a flame retardant leather-based triboelectric self-powered sensor.

[0018] like Figure 1 As shown, a flame-retardant leather-based triboelectric self-powered sensor of the present invention is constructed with octaamino cage silsesquioxane modified leather as a tribopositive layer, PTFE film as a tribone negative layer, and copper as an electrode layer; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0019] The method for preparing a flame-retardant leather-based triboelectric self-powered sensor of the present invention is specifically implemented according to the following steps: Step 1: immerse the leather in a salt solution (the salt solution is a sodium chloride solution with a mass concentration of 6 wt%-8 wt%), adjust the pH to 4.5, add octaamino cage silsesquioxane and shake for 1 h~2 h, slowly adjust the pH to 3.0 with a formic acid solution after the shaking, shake again for 1 h, then stand overnight, wash with water the next day, and naturally dry to obtain octaamino cage silsesquioxane modified leather; the mass ratio of leather to octaamino cage silsesquioxane is 1:0.8-4, and the mass ratio of leather to salt solution is: 1:2-2.5; Step 2: Using octaamino cage silsesquioxane modified leather as the triboelectric positive layer, PTFE film as the triboelectric negative layer, and copper as the electrode layer, a flame-retardant leather-based triboelectric self-powered sensor was constructed; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0020] Reference Figure 2The invention discloses a method for preparing a flame-retardant leather-based triboelectric self-powered sensor. The leather has the advantages of good flexibility and biodegradability. Octaamino cage silsesquioxane is introduced into the leather through leather wet processing technology to give the leather flame retardant properties. At the same time, its electron supply capacity is enhanced to improve the triboelectric sensing performance. The modified leather is used as a tribopositive layer and a polytetrafluoroethylene film is used as a tribopositive layer to construct a flame-retardant leather-based triboelectric self-powered sensor. The limiting oxygen index (LOI) value of the prepared octaamino cage silsesquioxane modified leather triboelectric positive layer material can reach 29.2%. The sensor shows high stability in a high temperature environment of 160°C, and the output retention rate reaches 88%.

[0021] Example 1 like Figure 1 As shown, a flame-retardant leather-based triboelectric self-powered sensor of the present invention is constructed with octaamino cage silsesquioxane modified leather as a tribopositive layer, PTFE film as a tribone negative layer, and copper as an electrode layer; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0022] The method for preparing a flame-retardant leather-based triboelectric self-powered sensor of the present invention is specifically implemented according to the following steps: Step 1: 10 g of leather was immersed in 20 mL of a 6 wt% sodium chloride solution, the pH was adjusted to 4.5, 0.8 g of octaamino cage silsesquioxane was added and shaken for 1 h, and after the shaking, the pH was slowly adjusted to 3.0 using a formic acid solution, and the mixture was shaken again for 1 h, and then allowed to stand overnight, and washed with water the next day, and dried naturally to obtain octaamino cage silsesquioxane modified leather; Step 2: Using octaamino cage silsesquioxane modified leather as the triboelectric positive layer, PTFE film as the triboelectric negative layer, and copper as the electrode layer, a flame-retardant leather-based triboelectric self-powered sensor was constructed; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0023] After testing, the limiting oxygen index (LOI) value of the octaamino cage silsesquioxane modified leather triboelectric positive layer material prepared in Example 1 can reach 28.7%. The sensor shows high stability in a high temperature environment of 160°C, and the output retention rate reaches 87%.

[0024] Example 2 like Figure 1As shown, a flame-retardant leather-based triboelectric self-powered sensor of the present invention is constructed with octaamino cage silsesquioxane modified leather as a tribopositive layer, PTFE film as a tribone negative layer, and copper as an electrode layer; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0025] The method for preparing a flame-retardant leather-based triboelectric self-powered sensor of the present invention is specifically implemented according to the following steps: Step 1: 10 g of leather was immersed in 20 mL of 8 wt% sodium chloride solution, the pH was adjusted to 4.5, 1.6 g of octaamino cage silsesquioxane was added and shaken for 1.5 h, and after the shaking, the pH was slowly adjusted to 3.0 with formic acid solution, and the mixture was shaken again for 1 h, and then allowed to stand overnight, and washed with water the next day, and dried naturally to obtain octaamino cage silsesquioxane modified leather; Step 2: Using octaamino cage silsesquioxane modified leather as the triboelectric positive layer, PTFE film as the triboelectric negative layer, and copper as the electrode layer, a flame-retardant leather-based triboelectric self-powered sensor was constructed; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0026] After testing, the limiting oxygen index (LOI) value of the octaamino cage silsesquioxane modified leather triboelectric positive layer material prepared in Example 2 can reach 28.8%. The sensor shows high stability in a high temperature environment of 160°C, and the output retention rate reaches 86%.

[0027] Example 3 like Figure 1 As shown, a flame-retardant leather-based triboelectric self-powered sensor of the present invention is constructed with octaamino cage silsesquioxane modified leather as a tribopositive layer, PTFE film as a tribone negative layer, and copper as an electrode layer; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0028] The method for preparing a flame-retardant leather-based triboelectric self-powered sensor of the present invention is specifically implemented according to the following steps: Step 1: 10 g of leather was immersed in 20 mL of a 7 wt% sodium chloride solution, the pH was adjusted to 4.5, 2.4 g of octaamino cage silsesquioxane was added and shaken for 1.5 h, and after the shaking, the pH was slowly adjusted to 3.0 using a formic acid solution, and the mixture was shaken again for 1 h, and then allowed to stand overnight, and washed with water the next day, and dried naturally to obtain octaamino cage silsesquioxane modified leather; Step 2: Using octaamino cage silsesquioxane modified leather as the triboelectric positive layer, PTFE film as the triboelectric negative layer, and copper as the electrode layer, a flame-retardant leather-based triboelectric self-powered sensor was constructed; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0029] After testing, the limiting oxygen index (LOI) value of the octaamino cage silsesquioxane modified leather triboelectric positive layer material prepared in Example 3 can reach 29%. The sensor shows high stability in a high temperature environment of 160°C, and the output retention rate reaches 87%.

[0030] Example 4 like Figure 1 As shown, a flame-retardant leather-based triboelectric self-powered sensor of the present invention is constructed with octaamino cage silsesquioxane modified leather as a tribopositive layer, PTFE film as a tribone negative layer, and copper as an electrode layer; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0031] The method for preparing a flame-retardant leather-based triboelectric self-powered sensor of the present invention is specifically implemented according to the following steps: Step 1: 10 g of leather was immersed in 20 mL of a 6 wt% sodium chloride solution, the pH was adjusted to 4.5, 3.2 g of octaamino cage silsesquioxane was added and shaken for 2 h, and after the shaking, the pH was slowly adjusted to 3.0 using a formic acid solution, and the mixture was shaken again for 1 h, and then allowed to stand overnight, and washed with water the next day, and dried naturally to obtain octaamino cage silsesquioxane modified leather; Step 2: Using octaamino cage silsesquioxane modified leather as the triboelectric positive layer, PTFE film as the triboelectric negative layer, and copper as the electrode layer, a flame-retardant leather-based triboelectric self-powered sensor was constructed; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0032] After testing, the limiting oxygen index (LOI) value of the octaamino cage silsesquioxane modified leather triboelectric positive layer material prepared in Example 4 can reach 29.1%. The sensor shows high stability in a high temperature environment of 160°C, and the output retention rate reaches 88%.

[0033] Example 5 like Figure 1As shown, a flame-retardant leather-based triboelectric self-powered sensor of the present invention is constructed with octaamino cage silsesquioxane modified leather as a tribopositive layer, PTFE film as a tribone negative layer, and copper as an electrode layer; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0034] The method for preparing a flame-retardant leather-based triboelectric self-powered sensor of the present invention is specifically implemented according to the following steps: Step 1: 10 g of leather was immersed in 20 mL of a 7 wt% sodium chloride solution, the pH was adjusted to 4.5, 4 g of octaamino cage silsesquioxane was added and shaken for 2 h, and after the shaking, the pH was slowly adjusted to 3.0 using a formic acid solution, and then shaken for 1 h, and then allowed to stand overnight, and washed with water the next day, and dried naturally to obtain octaamino cage silsesquioxane modified leather; Step 2: Using octaamino cage silsesquioxane modified leather as the triboelectric positive layer, PTFE film as the triboelectric negative layer, and copper as the electrode layer, a flame-retardant leather-based triboelectric self-powered sensor was constructed; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0035] After testing, the limiting oxygen index (LOI) value of the octaamino cage silsesquioxane modified leather triboelectric positive layer material prepared in Example 5 can reach 28.4%. The sensor shows high stability in a high temperature environment of 160°C, and the output retention rate reaches 85%.

[0036] Example 6 like Figure 1 As shown, a flame-retardant leather-based triboelectric self-powered sensor of the present invention is constructed with octaamino cage silsesquioxane modified leather as a tribopositive layer, PTFE film as a tribone negative layer, and copper as an electrode layer; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0037] The method for preparing a flame-retardant leather-based triboelectric self-powered sensor of the present invention is specifically implemented according to the following steps: Step 1: 10 g of leather was immersed in 20 mL of 8 wt% sodium chloride solution, the pH was adjusted to 4.5, 3.9 g of octaamino cage silsesquioxane was added and shaken for 2 h, and after the shaking, the pH was slowly adjusted to 3.0 with formic acid solution, and then shaken for 1 h, and then allowed to stand overnight, and washed with water the next day, and dried naturally to obtain octaamino cage silsesquioxane modified leather; Step 2: Using octaamino cage silsesquioxane modified leather as the triboelectric positive layer, PTFE film as the triboelectric negative layer, and copper as the electrode layer, a flame-retardant leather-based triboelectric self-powered sensor was constructed; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

[0038] After testing, the limiting oxygen index (LOI) value of the octaamino cage silsesquioxane modified leather triboelectric positive layer material prepared in Example 6 can reach 28.9%. The sensor shows high stability in a high temperature environment of 160°C, and the output retention rate reaches 88%.

Claims

1. Flame-retardant leather-based triboelectric self-powered sensor, characterized in that: The flame-retardant leather-based triboelectric self-powered sensor is constructed with octaamino cage silsesquioxane-modified leather as the tribopositive layer, PTFE film as the tribone negative layer, and copper as the electrode layer. Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

2. The method for preparing the flame-retardant leather-based triboelectric self-powered sensor according to claim 1, characterized in that: Follow the steps below to implement it: Step 1: immerse the leather in a salt solution, adjust the pH to 4.5, add octaamino cage silsesquioxane and shake, and after shaking, use a formic acid solution to slowly adjust the pH to 3.0, shake again, then wash with water and dry to obtain octaamino cage silsesquioxane modified leather; the mass ratio of leather to octaamino cage silsesquioxane is 1:0.8-4, and the mass ratio of leather to salt solution is: 1:2-2.5; Step 2: Using octaamino cage silsesquioxane modified leather as the triboelectric positive layer, PTFE film as the triboelectric negative layer, and copper as the electrode layer, a flame-retardant leather-based triboelectric self-powered sensor was constructed; Wherein: the electrode layer is arranged on one side of the positive electric layer and the negative electric layer, and the positive electric layer and the negative electric layer are connected by a wire.

3. The method for preparing the flame-retardant leather-based triboelectric self-powered sensor according to claim 2, characterized in that: In the step 1, the octaamino cage silsesquioxane is added and shaken for 1 h to 2 h.

4. The method for preparing the flame-retardant leather-based triboelectric self-powered sensor according to claim 3, characterized in that: In step 1, the shaking time is 1 hour.

5. The method for preparing the flame-retardant leather-based triboelectric self-powered sensor according to claim 4, characterized in that: In the step 1, washing with water is performed the next day.

6. The method for preparing the flame-retardant leather-based triboelectric self-powered sensor according to claim 5, characterized in that: In step 1, the drying is natural drying.

7. The method for preparing the flame-retardant leather-based triboelectric self-powered sensor according to claim 6, characterized in that: In the step 1, in the step 1, the mixture is shaken again and then allowed to stand overnight.

8. The method for preparing the flame-retardant leather-based triboelectric self-powered sensor according to claim 7, characterized in that: The salt solution is a sodium chloride solution with a mass concentration of 6 wt%-8 wt%.

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