High-humidity-resistant leather-based triboelectricity self-energized sensor and preparation method thereof

Abstract

The invention discloses a preparation method of a high-humidity-resistant leather-based triboelectric self-energy-supply sensor, which specifically comprises the following steps: taking leather as a flexible substrate, adopting a leather-making wet processing technology, selecting fluorine-containing polyhedral oligomeric silsesquioxane to modify the interior of leather collagen fibers, and further preparing the high-humidity-resistant leather-based triboelectric self-energy-supply sensor through a chemical vapor deposition method. Carrying out surface fluorination modification on the fluorine-containing polyhedral oligomeric silsesquioxane modified leather by using fluorine-containing siloxane to obtain fluorine-reinforced leather; and a polyamide film is used as a triboelectric positive layer, copper is used as an electrode layer, and the high-humidity-resistant leather-based triboelectric self-energized sensor is constructed. The high-humidity-resistant leather-based triboelectricity self-energized sensor prepared by the invention has extremely high sensitivity, and also shows relatively high stability in a high-humidity environment. When the relative humidity is increased from 10% to 90%, the open-circuit voltage is still maintained at 86% of the initial value. The method has important application value in the fields of intelligent wearable equipment, sensors, energy collection devices and the like.

Description

Technical Field

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

[0002] With the rapid development of flexible wearable devices and the intensification of energy crisis, multifunctional self-powered flexible sensors have emerged. As a new type of sensor based on contact electrification and electrostatic induction, triboelectric nanogenerator (TENG) has broad application prospects in the fields of self-powered sensing, micro-nano power sources, blue energy, etc. In order to better promote the practical application of triboelectric nanogenerators, friction materials are one of the key factors that determine their performance. In addition to good output performance, friction materials also need to have high humidity resistance to cope with the complexity and variability of the actual environment. At present, the friction materials of triboelectric self-powered flexible sensors are mostly synthetic polymers, which will cause harm to the environment when buried or incinerated as electronic waste; in addition, in harsh environments, especially under high humidity, the triboelectric output performance of TENG is severely limited due to the shielding effect of water molecules on the surface charge of the friction layer material. Therefore, selecting green and environmentally friendly friction materials to prepare high-output and high-humidity-resistant TENG is of great significance to promote its large-scale application. Summary of the invention

[0003] The first purpose of the present invention is to provide a high-humidity resistant leather-based friction electric self-powered sensor to solve the problem that the friction self-powered flexible sensor has poor stability in a high-humidity environment and is prone to environmental pollution.

[0004] To achieve the above purpose, the technical solution adopted by the present invention is: a high-humidity resistant leather-based triboelectric self-powered sensor is constructed with fluorine-reinforced leather as a triboelectric negative layer, a polyamide film as a triboelectric positive 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 purpose of the present invention is to provide a method for preparing a high-humidity resistant leather-based triboelectric self-powered sensor to solve the problem that the triboelectric self-powered flexible sensor has poor stability in a high-humidity environment and is prone to causing environmental pollution.

[0006] To achieve the above-mentioned purpose, the technical solution adopted by the present invention is: a method for preparing a high-humidity resistant leather-based triboelectric self-powered sensor, which is specifically implemented according to the following steps: Step 1: dissolving the fluorinated cage silsesquioxane in deionized water to obtain a fluorinated cage silsesquioxane solution, adding leather to the fluorinated cage silsesquioxane solution, and then shaking for 2 h to 4 h. After the shaking, adding sodium bicarbonate solution until the pH reaches 3.0 to 4.0, and finally heating to 40 ° C for reaction for 30 min to 40 min to obtain fluorinated cage silsesquioxane modified leather; Step 2: treating the fluorinated cage silsesquioxane modified leather by plasma technology to obtain hydroxylated fluorinated cage silsesquioxane modified leather; Step 3: preparing a fluorine-containing silane hydrolyzate, and after ultrasonic treatment, loading the fluorine-containing silane hydrolyzate onto the above-mentioned hydroxylated fluorine-containing cage-type silsesquioxane modified leather by chemical vapor deposition to obtain fluorine-reinforced leather; Step 4: Use fluorine-reinforced leather as the triboelectric negative layer, polyamide film as the triboelectric positive layer, and copper as the electrode layer to construct a high-humidity resistant leather-based triboelectric self-powered sensor.

[0007] In step 1, shaking was performed at 25°C.

[0008] In step 1, the shock is 10.5 r / min. In step 1, sodium bicarbonate solution is added in portions.

[0009] In step 1, there was an interval of 15 min between each addition of sodium bicarbonate solution.

[0010] In step 2, the fluorine-containing cage-type silsesquioxane-modified leather is treated by plasma technology, and the gas introduced is oxygen.

[0011] In step 2, the radio frequency power used for treating the fluorinated cage silsesquioxane modified leather by plasma technology is 80 kW-90 kW.

[0012] In step 2, the fluorinated cage silsesquioxane modified leather is treated by plasma technology for a treatment time of 300 s-420 s.

[0013] The beneficial effects of the present invention are as follows: the preparation method of the high-humidity resistant leather-based triboelectric self-powered sensor of the present invention, based on the advantages of leather such as good flexibility and biodegradability, introduces fluorinated cage-type silsesquioxane into leather through leather wet processing technology, enhances the electron-absorbing ability of leather, and improves its triboelectric sensing performance; at the same time, fluorinated silane is used to reduce the surface free energy of leather, give it hydrophobicity, prepare fluorine-reinforced leather, use it as a triboelectric negative layer, and polyamide film as a triboelectric positive layer to construct a high-humidity resistant leather-based triboelectric self-powered sensor. The sensor has extremely high sensitivity (2.38V / kPa) and still retains 86% of the original output in an environment with a relative humidity of up to 90%. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 It is a structural schematic diagram of a leather-based triboelectric self-powered sensor obtained by a method for preparing a high-humidity resistant leather-based triboelectric self-powered sensor of the present invention; Figure 2 It is a sensitivity diagram of a leather-based triboelectric self-powered sensor obtained by the preparation method of a high-humidity resistant leather-based triboelectric self-powered sensor of the present invention; Figure 3 This is an output performance diagram of a leather-based triboelectric self-powered sensor obtained by the method for preparing a high-humidity resistant leather-based triboelectric self-powered sensor of the present invention. 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] Leather is a polymer material with a natural hierarchical pore structure. It has advantages such as renewability, comfort and biodegradability, which is very consistent with the requirements of flexible smart wearable substrate materials. Fluorinated cage silsesquioxane (FPOSS for short) is a type of organic-inorganic hybrid material with a highly symmetrical nanoscale cubic cage skeleton. Its periphery contains abundant electron-withdrawing groups -F, which enhances the electron-withdrawing ability of the material. In addition, fluorinated silane can effectively reduce the free energy of the material surface, while improving the hydrophobicity of the material and the moisture resistance of the device.

[0017] The present invention proposes to use leather with advantages such as good flexibility and biodegradability as a sensing material, select fluorinated cage silsesquioxane to modify the inside of leather collagen fibers, and utilize the -F group on the fluorinated cage silsesquioxane to enhance the electron-withdrawing ability of the leather and improve its triboelectric sensing performance; utilize the excellent hydrophobicity of the fluorinated silane to give the leather high-humidity resistance, and obtain a high-humidity resistant leather-based triboelectric self-powered sensor.

[0018] The preparation method of the high-humidity resistant leather-based triboelectric self-powered sensor of the present invention is specifically implemented according to the following steps: Step 1: dissolving the fluorinated cage silsesquioxane in deionized water to obtain a fluorinated cage silsesquioxane solution, adding leather to the fluorinated cage silsesquioxane solution, and shaking at 25°C and 10.5 r / min for 2 h to 4 h, adding a certain amount of sodium bicarbonate solution to the system every 15 min after the shaking until the pH reaches 3.0 to 4.0, heating to 40°C and reacting for 30 min to 40 min to obtain fluorinated cage silsesquioxane modified leather; Step 2: treating the fluorinated cage-type silsesquioxane-modified leather by plasma technology (the gas introduced is oxygen, the radio frequency power is 80 kW-90 kW, and the treatment time is 300 s-420 s) to obtain hydroxylated fluorinated cage-type silsesquioxane-modified leather; Step 3: preparing a fluorine-containing silane hydrolyzate, and after ultrasonic treatment, loading the fluorine-containing silane hydrolyzate onto the above-mentioned hydroxylated fluorine-containing cage-type silsesquioxane modified leather by chemical vapor deposition to obtain fluorine-reinforced leather; Step 4: Using fluorine-reinforced leather as the triboelectric negative layer, polyamide film as the triboelectric positive layer, and copper as the electrode layer, a high-humidity-resistant leather-based triboelectric self-powered sensor was constructed; Figure 1 As shown, the electrode layer is arranged on one side of the positive layer and the negative layer, and the other side of the positive layer and the negative layer are connected by a wire.

[0019] Reference Figure 2 and Figure 3 The invention discloses a method for preparing a high-humidity-resistant leather-based triboelectric self-powered sensor. Based on the advantages of leather such as good flexibility and biodegradability, fluorinated cage-type silsesquioxane is introduced into leather through leather wet processing technology to enhance the leather's electron-absorbing ability and improve its triboelectric sensing performance. At the same time, fluorinated silane is used to reduce the surface free energy of leather and give it hydrophobicity, and fluorine-reinforced leather is prepared, which is used as a triboelectric negative layer and a polyamide film as a triboelectric positive layer to construct a high-humidity-resistant leather-based triboelectric self-powered sensor. The sensor has an extremely high sensitivity of up to 2.38 V / kPa, and can still retain 86% of the original output in an environment with a relative humidity of up to 90%.

[0020] Example 1 like Figure 1 As shown, the high-humidity resistant leather-based triboelectric self-powered sensor of the present invention is constructed with fluorine-reinforced leather as the triboelectric negative layer, polyamide film as the triboelectric positive 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.

[0021] The preparation method of the high-humidity resistant leather-based triboelectric self-powered sensor of the present invention is specifically implemented according to the following steps: Step 1: 4 mL of fluorinated cage silsesquioxane and 10 g of leather were added to 20 mL of deionized water, respectively, and shaken at room temperature for 2 h. After shaking, the pH value of the solution was slowly adjusted to 3.0 with sodium bicarbonate solution, and then shaken for another 1 h to obtain fluorinated cage silsesquioxane-modified leather; Step 2: treating the fluorinated cage silsesquioxane modified leather by plasma technology (the gas introduced is oxygen, the radio frequency power is 80 kW, and the treatment time is 420 s) to obtain hydroxylated fluorinated cage silsesquioxane modified leather; Step 3: preparing 30 g of fluorinated silane hydrolyzate (mass concentration 1 wt%), and after ultrasonic treatment, loading the fluorinated silane hydrolyzate onto the above-mentioned hydroxylated fluorinated cage-type silsesquioxane modified leather by chemical vapor deposition to obtain fluorine-reinforced leather; Step 4: Use fluorine-reinforced leather as the triboelectric negative layer, polyamide film as the triboelectric positive layer, and copper as the electrode layer to construct a high-humidity resistant leather-based triboelectric self-powered sensor.

[0022] like Figure 1 As shown, the electrode layer is set on one side of the positive layer and the negative layer, and the other side of the positive layer and the negative layer are connected by a wire. The test verified that the sensor has an extremely high sensitivity of 2.33 V / kPa, and still retains 86% of the original output in an environment with a relative humidity of up to 90%.

[0023] Example 2 like Figure 1 As shown, the high-humidity resistant leather-based triboelectric self-powered sensor of the present invention is constructed with fluorine-reinforced leather as the triboelectric negative layer, polyamide film as the triboelectric positive 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.

[0024] The preparation method of the high-humidity resistant leather-based triboelectric self-powered sensor of the present invention is specifically implemented according to the following steps: Step 1: Add 5 mL of fluorinated cage silsesquioxane and 10 g of leather into 20 mL of deionized water, shake at room temperature for 3 h, and then slowly adjust the pH of the solution to 3.0 with sodium bicarbonate solution, and shake for another 2 h to obtain fluorinated cage silsesquioxane modified leather; Step 2: treating the fluorinated cage silsesquioxane modified leather by plasma technology (the gas introduced is oxygen, the radio frequency power is 90 kW, and the treatment time is 360 s) to obtain hydroxylated fluorinated cage silsesquioxane modified leather; Step 3: preparing 30 g of fluorinated silane hydrolyzate (mass concentration 2 wt%), and after ultrasonic treatment, loading the fluorinated silane hydrolyzate onto the hydroxylated fluorinated cage-type silsesquioxane modified leather by chemical vapor deposition to obtain fluorine-reinforced leather; Step 4: Use fluorine-reinforced leather as the triboelectric negative layer, polyamide film as the triboelectric positive layer, and copper as the electrode layer to construct a high-humidity resistant leather-based triboelectric self-powered sensor.

[0025] like Figure 1 As shown, the electrode layer is set on one side of the positive layer and the negative layer, and the other side of the positive layer and the negative layer are connected by a wire. The test verified that the sensor has an extremely high sensitivity of 2.35 V / kPa, and still retains 84% ​​of the original output in an environment with a relative humidity of up to 90%.

[0026] Example 3 like Figure 1 As shown, the high-humidity resistant leather-based triboelectric self-powered sensor of the present invention is constructed with fluorine-reinforced leather as the triboelectric negative layer, polyamide film as the triboelectric positive 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.

[0027] The preparation method of the high-humidity resistant leather-based triboelectric self-powered sensor of the present invention is specifically implemented according to the following steps: Step 1: Add 6 mL of fluorinated cage silsesquioxane and 10 g of leather into 20 mL of deionized water, shake at room temperature for 3 h, and then slowly adjust the pH of the solution to 3.5 with sodium bicarbonate solution, and shake for another 2 h to obtain fluorinated cage silsesquioxane modified leather; Step 2: treating the fluorinated cage silsesquioxane modified leather by plasma technology (the gas introduced is oxygen, the radio frequency power is 90 kW, and the treatment time is 420 s) to obtain hydroxylated fluorinated cage silsesquioxane modified leather; Step 3: preparing 30 g of fluorinated silane hydrolyzate (mass concentration 3 wt%), and after ultrasonic treatment, loading the fluorinated silane hydrolyzate onto the hydroxylated fluorinated cage-type silsesquioxane modified leather by chemical vapor deposition to obtain fluorine-reinforced leather; Step 4: Using the fluorine-reinforced leather as the triboelectric negative layer, the polyamide film as the triboelectric positive layer, and copper as the electrode layer, a high-humidity resistant leather-based triboelectric self-powered sensor is constructed.

[0028] like Figure 1 As shown, the electrode layer is set on one side of the positive layer and the negative layer, and the other side of the positive layer and the negative layer are connected by a wire. The test verified that the sensor has an extremely high sensitivity of 2.38 V / kPa, and still retains 86% of the original output in an environment with a relative humidity of up to 90%.

[0029] Example 4 like Figure 1As shown, the high-humidity resistant leather-based triboelectric self-powered sensor of the present invention is constructed with fluorine-reinforced leather as the triboelectric negative layer, polyamide film as the triboelectric positive 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.

[0030] The preparation method of the high-humidity resistant leather-based triboelectric self-powered sensor of the present invention is specifically implemented according to the following steps: Step 1: Add 7 mL of fluorinated cage silsesquioxane and 10 g of leather into 20 mL of deionized water, shake at room temperature for 4 h, and then slowly adjust the pH of the solution to 3.5 with sodium bicarbonate solution, and shake for another 2 h to obtain fluorinated cage silsesquioxane modified leather; Step 2: treating the fluorinated cage silsesquioxane modified leather by plasma technology (the gas introduced is oxygen, the radio frequency power is 90 kW, and the treatment time is 360 s) to obtain hydroxylated fluorinated cage silsesquioxane modified leather; Step 3: preparing 30 g of fluorinated silane hydrolyzate (mass concentration 4 wt%), and after ultrasonic treatment, loading the fluorinated silane hydrolyzate onto the hydroxylated fluorinated cage-type silsesquioxane modified leather by chemical vapor deposition to obtain fluorine-reinforced leather; Step 4: Use fluorine-reinforced leather as the triboelectric negative layer, polyamide film as the triboelectric positive layer, and copper as the electrode layer to construct a high-humidity resistant leather-based triboelectric self-powered sensor.

[0031] like Figure 1 As shown, the electrode layer is set on one side of the positive layer and the negative layer, and the other side of the positive layer and the negative layer are connected by a wire. The sensor has been tested and verified to have an extremely high sensitivity of 2.29 V / kPa, and still retains 85% of the original output in an environment with a relative humidity of up to 90%.

[0032] Example 5 like Figure 1 As shown, the high-humidity resistant leather-based triboelectric self-powered sensor of the present invention is constructed with fluorine-reinforced leather as the triboelectric negative layer, polyamide film as the triboelectric positive 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.

[0033] The preparation method of the high-humidity resistant leather-based triboelectric self-powered sensor of the present invention is specifically implemented according to the following steps: Step 1: Add 7.5 mL of fluorinated cage silsesquioxane and 10 g of leather into 20 mL of deionized water, shake at room temperature for 4 h, and after shaking, slowly adjust the solution pH to 3.5 with sodium bicarbonate solution, and shake for another 2 h to obtain fluorinated cage silsesquioxane modified leather; Step 2: treating the fluorinated cage silsesquioxane modified leather by plasma technology (the gas introduced is oxygen, the radio frequency power is 90 kW, and the treatment time is 420 s) to obtain hydroxylated fluorinated cage silsesquioxane modified leather; Step 3: preparing 30 g of fluorinated silane hydrolyzate (mass concentration 5 wt%), and after ultrasonic treatment, loading the fluorinated silane hydrolyzate onto the hydroxylated fluorinated cage-type silsesquioxane modified leather by chemical vapor deposition to obtain fluorine-reinforced leather; Step 4: Use fluorine-reinforced leather as the triboelectric negative layer, polyamide film as the triboelectric positive layer, and copper as the electrode layer to construct a high-humidity resistant leather-based triboelectric self-powered sensor.

[0034] like Figure 1 As shown, the electrode layer is set on one side of the positive layer and the negative layer, and the other side of the positive layer and the negative layer are connected by a wire. The test verified that the sensor has an extremely high sensitivity of 2.31 V / kPa, and still retains 84% ​​of the original output in an environment with a relative humidity of up to 90%.

[0035] Example 6 like Figure 1 As shown, the high-humidity resistant leather-based triboelectric self-powered sensor of the present invention is constructed with fluorine-reinforced leather as the triboelectric negative layer, polyamide film as the triboelectric positive 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.

[0036] The preparation method of the high-humidity resistant leather-based triboelectric self-powered sensor of the present invention is specifically implemented according to the following steps: Step 1: 8 mL of fluorinated cage silsesquioxane and 10 g of leather were added to 20 mL of deionized water, respectively, and shaken at room temperature for 4 h. After shaking, the pH value of the solution was slowly adjusted to 3.5 with sodium bicarbonate solution, and then shaken for another 2 h to obtain fluorinated cage silsesquioxane modified leather; Step 2: treating the fluorinated cage silsesquioxane modified leather by plasma technology (the gas introduced is oxygen, the radio frequency power is 90 kW, and the treatment time is 420 s) to obtain hydroxylated fluorinated cage silsesquioxane modified leather; Step 3: preparing 30 g of fluorinated silane hydrolyzate (mass concentration 5 wt%), and after ultrasonic treatment, loading the fluorinated silane hydrolyzate onto the hydroxylated fluorinated cage-type silsesquioxane modified leather by chemical vapor deposition to obtain fluorine-reinforced leather; Step 4: Use fluorine-reinforced leather as the triboelectric negative layer, polyamide film as the triboelectric positive layer, and copper as the electrode layer to construct a high-humidity resistant leather-based triboelectric self-powered sensor.

[0037] like Figure 1 As shown, the electrode layer is set on one side of the positive layer and the negative layer, and the other side of the positive layer and the negative layer are connected by a wire. The test has verified that the sensor has an extremely high sensitivity of 2.37 V / kPa, and still retains 86% of the original output in an environment with a relative humidity of up to 90%.

Claims

1. A high humidity resistant leather-based triboelectric self-powered sensor, characterized in that: The high-humidity-resistant leather-based triboelectric self-powered sensor is constructed with fluorine-reinforced leather as the triboelectric negative layer, polyamide film as the triboelectric positive 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 high humidity resistant leather-based triboelectric self-powered sensor according to claim 1, characterized in that: Follow the steps below to implement it: Step 1: dissolving the fluorinated cage silsesquioxane in deionized water to obtain a fluorinated cage silsesquioxane solution, adding leather to the fluorinated cage silsesquioxane solution, and then shaking for 2 h to 4 h. After the shaking, adding sodium bicarbonate solution until the pH reaches 3.0 to 4.0, and finally heating to 40 ° C for reaction for 30 min to 40 min to obtain fluorinated cage silsesquioxane modified leather; Step 2: treating the fluorinated cage silsesquioxane modified leather by plasma technology to obtain hydroxylated fluorinated cage silsesquioxane modified leather; Step 3: preparing a fluorine-containing silane hydrolyzate, and after ultrasonic treatment, loading the fluorine-containing silane hydrolyzate onto the above-mentioned hydroxylated fluorine-containing cage-type silsesquioxane modified leather by chemical vapor deposition to obtain fluorine-reinforced leather; Step 4: Use fluorine-reinforced leather as the triboelectric negative layer, polyamide film as the triboelectric positive layer, and copper as the electrode layer to construct a high-humidity resistant leather-based triboelectric self-powered sensor; the electrode layer is set on one side of the positive layer and the negative layer, and the other side of the positive layer and the negative layer are connected by a wire.

3. The method for preparing the high humidity resistant leather-based triboelectric self-powered sensor according to claim 2, characterized in that: In the step 1, shaking was performed at 25°C.

4. The method for preparing the high humidity resistant leather-based triboelectric self-powered sensor according to claim 3, characterized in that: In the step 1, the oscillation is 10.5 r / min.

5. The method for preparing the high humidity resistant leather-based triboelectric self-powered sensor according to claim 4, characterized in that: In the step 1, the sodium bicarbonate solution is added in portions.

6. The method for preparing the high humidity resistant leather-based triboelectric self-powered sensor according to claim 5, characterized in that: In step 1, the sodium bicarbonate solution was added each time with an interval of 15 minutes.

7. The method for preparing the high humidity resistant leather-based triboelectric self-powered sensor according to claim 6, characterized in that: In the step 2, the fluorinated cage-type silsesquioxane-modified leather is treated by plasma technology, and the gas introduced is oxygen.

8. The method for preparing the high humidity resistant leather-based triboelectric self-powered sensor according to claim 7, characterized in that: In the step 2, the radio frequency power used for treating the fluorinated cage silsesquioxane modified leather by plasma technology is 80 kW to 90 kW.

9. The method for preparing the high humidity resistant leather-based triboelectric self-powered sensor according to claim 8, characterized in that: In the step 2, the fluorinated cage-type silsesquioxane-modified leather is treated by plasma technology for a treatment time of 300 s-420 s.

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