Method for preparing leather-based triboelectric nanogenerator with high output performance

Abstract

The application discloses a preparation method of a leather-based friction nanogenerator with high output performance, and comprises the following steps: S1, preparing a polycarboxyl cage-type silsesquioxane solution; S2, adding the polycarboxyl cage-type silsesquioxane solution and leather into deionized water and oscillating, adding a pyrrole monomer and a ferric chloride solution, ultrasonic cleaning after deionized water washing, and obtaining an LCF-PCOOH@PPy composite material; and S3, taking the LCF-PCOOH@PPy composite material as a friction positive layer, taking a polymer film PDMS as a friction negative layer, taking copper as an electrode layer, and constructing an (LCF-PCOOH@PPy) / PDMS friction nanogenerator. The preparation method of the leather-based friction nanogenerator with high output performance solves the problems of large internal resistance of the friction nanogenerator and serious material loss of the friction layer in the triboelectric process, thereby limiting the output and the durability of the friction nanogenerator.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of friction nanogenerators, and relates to a preparation method of a leather-based friction nanogenerator with high output performance. BACKGROUND

[0002] The rapid development of flexible wearable devices has led to an increase in electronic waste and environmental pollution due to regular battery replacement. Therefore, the development of flexible self-powered devices is of great significance to the green transformation of energy and the realization of the double carbon goal. A friction nanogenerator (TENG) is a miniaturized energy harvesting device based on contact electrification and electrostatic induction coupling effect, which is used in wearable electronic products. However, the large internal resistance and serious wear of the friction layer material during the tribocharging process limit the output and durability of the TENG.

[0003] Leather is a kind of polymer material with natural hierarchical porous structure, which has excellent hygiene and mechanical properties and has been used as wearable products for a long time. In addition, the thickness of leather can slow down the friction wear of the material, and its porous structure gives the material a high specific surface area, which can avoid the problem of performance reduction caused by thickness. Therefore, using leather as a friction layer material has great advantages. Polypyrrole (PPy) is an organic conjugated polymer material, which has been widely concerned in the fields of sensors, batteries, etc. due to its high conductivity, flexibility, low cost and good biocompatibility. PPy has high specific capacitance and fast redox reaction rate, which can realize fast charge storage. At the same time, due to the semiconductor property of PPy, it has a certain charge transfer capacity. Carboxylated cage silsesquioxane (PCOOH) is an organic-inorganic hybrid nanoparticle with a three-dimensional polyhedral structure, which has multiple organic functional group vertices and can realize the functional adjustment of the material. At the same time, studies have shown that using PCOOH as a dopant can improve the charge transfer capacity of PPy, but specific research in this regard is less. SUMMARY

[0004] The purpose of the present application is to provide a preparation method of a leather-based friction nanogenerator with high output performance, which solves the problem of large internal resistance and serious wear of the friction layer material during the tribocharging process of the friction nanogenerator in the prior art, thereby limiting the output and durability of the friction nanogenerator.

[0005] The technical solution adopted by the present application is a preparation method of a leather-based friction nanogenerator with high output performance, and the specific steps are as follows:

[0006] Step 1: Prepare a polycarboxyl cage silsesquioxane solution;

[0007] Step 2: The polycarboxyl cage silsesquioxane solution and the leather are added into deionized water respectively, and shaken for 1-2 hours at room temperature, then pyrrole monomer is added for stirring reaction, and then the ferric chloride solution is added, and after reaction for 2-4 hours, the LCF-PCOOH@PPy composite material is obtained after washing with deionized water and ultrasonic cleaning;

[0008] Step 3: The LCF-PCOOH@PPy composite material is used as a friction positive layer, the polymer film PDMS is used as a friction negative layer, and copper is used as an electrode layer to construct a (LCF-PCOOH@PPy) / PDMS triboelectric nanogenerator.

[0009] The application also has the characteristics that:

[0010] The specific steps for preparing the polycarboxyl cage silsesquioxane solution are as follows:

[0011] Step 1.1: The octavinyl cage silsesquioxane is dissolved in tetrahydrofuran to obtain solution A, and sodium dodecyl sulfate is dissolved in water to obtain solution B, and then ammonium persulfate, sodium bisulfite and methyl methacrylate are sequentially dissolved in deionized water to obtain solution C.

[0012] Step 1.2: Solution A and solution B are mixed and stirred, then solution C is added, and after stirring reaction again, the polycarboxyl cage silsesquioxane solution is obtained.

[0013] In step 1.1, the mass ratio of the octavinyl cage silsesquioxane to tetrahydrofuran is 1:390-410, the concentration of solution B is 0.035-0.038 g / mL, the concentration of ammonium persulfate is 0.048-0.078 g / mL, the concentration of sodium bisulfite is 0.032-0.049 g / mL, and the concentration of methyl methacrylate is 0.12-0.18 g / mL.

[0014] In step 1.2, the stirring reaction temperature of the mixture of solution A and solution B is 50-60 DEG C, and the reaction time is 25-35 min.

[0015] In step 1.2, the specific method for adding solution C is as follows: first, 1 / 3 of solution C is added, and stirring reaction is carried out at 50-60 DEG C for 25-35 min, then 1 / 3 of solution C is added, and stirring reaction is carried out at 50-60 DEG C for 25-35 min, and finally the remaining solution C is added, and stirring reaction is carried out at 50-60 DEG C for 200-230 min.

[0016] In step 2, the amount of the polycarboxyl cage silsesquioxane solution corresponding to each gram of leather is 1-9 mL, the volume ratio of the polycarboxyl cage silsesquioxane solution to deionized water is 0.02-0.18:1, the mass ratio of the pyrrole monomer to the leather is 0.25-1.25:1, and the molar ratio of the pyrrole monomer to the ferric chloride is 1:4.

[0017] The stirring temperature of the reaction after adding the pyrrole monomer in step 2 is 0-4 DEG C, and the reaction time is 1-2 h.

[0018] The iron chloride solution is added at a speed of 1-3 drops / s in step 2.

[0019] The ultrasonic cleaning time is 10-30 min.

[0020] The present application has the following beneficial effects:

[0021] The present application is based on the advantages of good flexibility, hygiene and mechanical properties of leather. PCOOH and PPy are introduced into the leather in turn by impregnation and in-situ polymerization, providing effective charge storage sites. The doping of PCOOH to PPy can further improve the conductivity of PPy. The LCF-PCOOH@PPy composite material with good charge storage and transmission performance is prepared. The (LCF-PCOOH@PPy) / PDMS triboelectric nanogenerator is constructed by taking the LCF-PCOOH@PPy as the positive triboelectric layer and the PDMS as the negative triboelectric layer, which has high output and durability. The short-circuit current is 0.4 mu A, and the open-circuit voltage is 308 V. At the same time, the signal output is stable under 20000 cycles. DETAILED DESCRIPTION

[0022] The present application will be described in detail below in conjunction with the specific embodiments.

[0023] The preparation method of the leather-based triboelectric nanogenerator with high output performance of the present application is as follows:

[0024] Step 1: Preparation of polycarboxyl cage-shaped silsesquioxane solution

[0025] Step 1.1: Dissolve octavinyl cage-shaped silsesquioxane (POSS-Vi) in tetrahydrofuran (THF), wherein the mass ratio of octavinyl cage-shaped silsesquioxane to tetrahydrofuran is 1:390-410, to obtain solution A; dissolve sodium dodecyl sulfate (SDS) in water, and the concentration of solution B is 0.035-0.038 g / mL, to obtain solution B; dissolve ammonium persulfate (APS), sodium bisulfite (RH) and methyl methacrylate (MMA) in deionized water in sequence, wherein the concentration of ammonium persulfate is 0.048-0.078 g / mL, the concentration of sodium bisulfite is 0.032-0.049 g / mL, and the concentration of methyl methacrylate is 0.12-0.18 g / mL, to obtain solution C.

[0026] Step 1.2: After mixing solution A and solution B, the reaction is stirred at a temperature of 50-60 DEG C for 25-35 min, then solution C is added, specifically, 1 / 3 of solution C is added first, and the reaction is stirred at 50-60 DEG C for 25-35 min, then 1 / 3 of solution C is added, and the reaction is stirred at 50-60 DEG C for 25-35 min, and finally the remaining solution C is added, and the reaction is stirred at 50-60 DEG C for 200-230 min, to obtain a polycarboxyl cage silsesquioxane (PCOOH) solution.

[0027] Step 2: The polycarboxyl cage silsesquioxane (PCOOH) solution and the leather are added to deionized water respectively, wherein the amount of the polycarboxyl cage silsesquioxane solution corresponding to each gram of leather is 1-9 mL; the volume ratio of the polycarboxyl cage silsesquioxane solution to deionized water is 0.02-0.18:1, and the mixture is shaken at room temperature for 1-9 h, then the pyrrole monomer (Py) is added and stirred to react at a temperature of 0-4 DEG C for 1-2 h, then the ferric chloride (FeCl3) solution is added dropwise at a speed of 1-3 drops / s, the mass ratio of the pyrrole monomer to the leather is 0.25-1.25:1, the molar ratio of the pyrrole monomer to the ferric chloride is 1:4, and the reaction is carried out for 2-4 h, then the product is washed with deionized water and ultrasonically cleaned for 10-30 min, to obtain an LCF-PCOOH@PPy composite material;

[0028] Step 3: The LCF-PCOOH@PPy composite material is used as a friction positive layer, a polymer film PDMS is used as a friction negative layer, and copper is used as an electrode layer, to construct an (LCF-PCOOH@PPy) / PDMS triboelectric nanogenerator.

[0029] The leather with a multi-scale hierarchical structure is selected as a base material, carboxylated cage silsesquioxane (PCOOH) with a hollow cage structure and polypyrrole (PPy) are sequentially introduced into the leather by impregnation and in-situ polymerization, the PCOOH increases the charge storage sites of the leather collagen fibers (LCF), and the PPy enhances the conductivity of the LCF, to obtain an LCF-PCOOH@PPy composite material with excellent charge storage and transmission performance; the LCF-PCOOH@PPy composite material is used as a friction positive layer, a polydimethylsiloxane film (PDMS) is used as a friction negative layer, and an (LCF-PCOOH@PPy) / PDMS triboelectric nanogenerator is constructed.

[0030] Example 1

[0031] The preparation method of the leather-based triboelectric nanogenerator with high output performance comprises the following specific steps:

[0032] Step 1: Preparation of a polycarboxyl cage silsesquioxane solution;

[0033] Step 1.1: 0.29 g of POSS-Vi was dissolved in 113.5 g of tetrahydrofuran to obtain solution A; 1.44 g of SDS was dissolved in water to obtain a SDS solution with a concentration of 0.035 g / mL, to obtain solution B; 9.6 g of APS, 6.4 g of RH, and 24 g of MMA were sequentially dissolved in 200 mL of deionized water to obtain solution C;

[0034] Step 1.2: After mixing solution A and solution B, stirring reaction was carried out at a reaction temperature of 50°C for 25 min, then solution C was added, specifically 1 / 3 of solution C was added first, stirring reaction was carried out at 60°C for 25 min, then 1 / 3 of solution C was added, stirring reaction was carried out at 60°C for 25 min, finally the remaining solution C was added, stirring reaction was carried out at 60°C for 200 min, to obtain a polycarboxyl cage silsesquioxane solution.

[0035] Step 2: 1 mL of the polycarboxyl cage silsesquioxane solution and 1 g of leather were added to 50 mL of deionized water respectively, and shaken at room temperature for 1 h, then 0.25 g of Py was added for stirring reaction, the reaction temperature was 0°C, and the reaction time was 1 h, then the ferric chloride solution was added dropwise at a speed of 1 drop / s, the molar ratio of pyrrole monomer to ferric chloride was 1:4, after reaction for 2 h, deionized water washing and ultrasonic cleaning were carried out for 30 min, to obtain an LCF-PCOOH@PPy composite material;

[0036] Step 3: The LCF-PCOOH@PPy composite material was used as a rubbing positive layer, the polymer film PDMS was used as a rubbing negative layer, and copper was used as an electrode layer to construct a (LCF-PCOOH@PPy) / PDMS triboelectric nanogenerator.

[0037] Example 2

[0038] The preparation method of the leather-based triboelectric nanogenerator with high output performance is as follows:

[0039] Step 1: Preparation of a polycarboxyl cage silsesquioxane solution;

[0040] Step 1.1: 0.29 g of POSS-Vi was dissolved in 118 g of tetrahydrofuran to obtain solution A; 1.44 g of SDS was dissolved in water to obtain a SDS solution with a concentration of 0.038 g / mL, to obtain solution B; 15.6 g of APS, 9.8 g of RH, and 36 g of MMA were sequentially dissolved in 200 mL of deionized water to obtain solution C;

[0041] Step 1.2: After mixing solution A and solution B, the stirring reaction was carried out, the reaction temperature was 60℃, the reaction time was 35min, then solution C was added, specifically 1 / 3 of solution C was added first, stirring reaction at 50℃ for 35min, then 1 / 3 of solution C was added, stirring reaction at 50℃ for 35min, finally the remaining solution C was added, stirring reaction at 50℃ for 230min, to obtain a polycarboxyl cage silsesquioxane solution.

[0042] Step 2: 9mL of polycarboxyl cage silsesquioxane solution and 1g of leather were added to 50mL of deionized water respectively, and shaken at room temperature for 3h, then 1.25g of Py was added and stirred, the reaction temperature was 4℃, the reaction time was 2h, then the ferric chloride solution was added at a speed of 3 drops / s, the molar ratio of pyrrole monomer to ferric chloride was 1:4, after reaction for 4h, the LCF-PCOOH@PPy composite material was obtained by washing with deionized water and ultrasonic cleaning for 10min;

[0043] Step 3: The LCF-PCOOH@PPy composite material was used as the rubbing positive layer, the polymer film PDMS was used as the rubbing negative layer, and copper was used as the electrode layer to construct the (LCF-PCOOH@PPy) / PDMS triboelectric nanogenerator.

[0044] Example 3

[0045] The preparation method of the leather-based triboelectric nanogenerator with high output performance is as follows:

[0046] Step 1: Preparation of polycarboxyl cage silsesquioxane solution;

[0047] Step 1.1: 0.29g of POSS-Vi was dissolved in 116g of tetrahydrofuran to obtain solution A; 1.44g of SDS was dissolved in water, the concentration of SDS solution was 0.036g / mL to obtain solution B; 12g of APS, 6g of RH and 30g of MMA were sequentially dissolved in 200mL of deionized water to obtain solution C;

[0048] Step 1.2: After mixing solution A and solution B, the stirring reaction was carried out, the reaction temperature was 55℃, the reaction time was 30min, then solution C was added, specifically 1 / 3 of solution C was added first, stirring reaction at 55℃ for 30min, then 1 / 3 of solution C was added, stirring reaction at 55℃ for 30min, finally the remaining solution C was added, stirring reaction at 55℃ for 220min, to obtain a polycarboxyl cage silsesquioxane solution.

[0049] Step 2: 5 mL of polycarboxyl cage silsesquioxane solution and 1 g of leather were added to 50 mL of deionized water, respectively, and shaken at room temperature for 5 h, then 0.75 g of Py was added to stir the reaction, the reaction temperature was 2 ℃, the reaction time was 2 h, and then the iron chloride solution was added at a speed of 2 drops / s, the molar ratio of pyrrole monomer to iron chloride was 1:4, and after 3 h of reaction, it was washed with deionized water and ultrasonic cleaning, the ultrasonic cleaning time was 20 min, to obtain the LCF-PCOOH@PPy composite material;

[0050] Step 3: The LCF-PCOOH@PPy composite material was used as the rubbing positive layer, the polymer film PDMS was used as the rubbing negative layer, and copper was used as the electrode layer to construct the (LCF-PCOOH@PPy) / PDMS triboelectric nanogenerator.

[0051] Example 4

[0052] The preparation method of the leather-based triboelectric nanogenerator with high output performance is as follows:

[0053] Step 1 is the same as step 1 of example 3;

[0054] Step 2: 7 mL of polycarboxyl cage silsesquioxane solution and 1 g of leather were added to 50 mL of deionized water, respectively, and shaken at room temperature for 7 h, then 1.0 g of Py was added to stir the reaction, the reaction temperature was 4 ℃, the reaction time was 2 h, and then the iron chloride solution was added at a speed of 1 drop / s, the molar ratio of pyrrole monomer to iron chloride was 1:4, and after 2.5 h of reaction, it was washed with deionized water and ultrasonic cleaning, the ultrasonic cleaning time was 30 min, to obtain the LCF-PCOOH@PPy composite material;

[0055] Step 3 is the same as step 3 of example 3.

[0056] Example 5

[0057] The preparation method of the leather-based triboelectric nanogenerator with high output performance is as follows:

[0058] Step 1 is the same as step 1 of example 3;

[0059] Step 2: 3 mL of polycarboxyl cage silsesquioxane solution and 1 g of leather were added to 50 mL of deionized water, respectively, and shaken at room temperature for 3 h, then 0.5 g of Py was added to stir the reaction, the reaction temperature was 1 ℃, the reaction time was 2 h, and then the iron chloride solution was added at a speed of 1 drop / s, the molar ratio of pyrrole monomer to iron chloride was 1:4, and after 3.5 h of reaction, it was washed with deionized water and ultrasonic cleaning, the ultrasonic cleaning time was 15 min, to obtain the LCF-PCOOH@PPy composite material;

[0060] Step 3 is the same as step 3 of example 3.

[0061] The output performance and cycle stability of the (LCF-PCOOH@PPy) / PDMS triboelectric nanogenerator prepared in Examples 1-5 were tested, and the results are as follows:

[0062] The short-circuit current of Example 1 was 0.12 μA, the open-circuit voltage was 100 V, and there was stable signal output under 20000 cycles;

[0063] The short-circuit current of Example 2 was 0.18 μA, the open-circuit voltage was 175 V, and there was stable signal output under 20000 cycles;

[0064] The short-circuit current of Example 3 was 0.3 μA, the open-circuit voltage was 275 V, and there was stable signal output under 20000 cycles;

[0065] The short-circuit current of Example 4 was 0.25 μA, the open-circuit voltage was 210 V, and there was stable signal output under 20000 cycles;

[0066] The short-circuit current of Example 5 was 0.4 μA, the open-circuit voltage was 308 V, and there was stable signal output under 20000 cycles;

[0067] The above results show that the (LCF-PCOOH@PPy) / PDMS triboelectric nanogenerator prepared in the present application has good cycle stability, and its output performance is significantly improved after optimization.

Claims

1. A method for preparing a leather-based tribo-nanogenerator with high output performance, characterized in that, The specific steps are as follows: Step 1: preparing a polycarboxyl cage silsesquioxane solution; Step 2: respectively adding the polycarboxyl cage silsesquioxane solution and leather into deionized water, oscillating at room temperature for 1-2 h, then adding pyrrole monomer for stirring reaction, and then adding ferric chloride solution, washing with deionized water after reaction for 2-4 h, and ultrasonic cleaning to obtain LCF-PCOOH@PPy composite material; Step 3: using the LCF-PCOOH@PPy composite material as a rubbing positive layer, using a polymer film PDMS as a rubbing negative layer, and using copper as an electrode layer to construct a (LCF-PCOOH@PPy) / PDMS rubbing nanogenerator; The specific steps for preparing the polycarboxyl cage silsesquioxane solution are as follows: Step 1.1: dissolving octavinyl cage silsesquioxane in tetrahydrofuran to obtain solution A, dissolving sodium dodecyl sulfate in water to obtain solution B, and sequentially dissolving ammonium persulfate, sodium bisulfite and methyl methacrylate in deionized water to obtain solution C; Step 1.2: mixing solution A and solution B for stirring reaction, then adding solution C, and stirring again to obtain a polycarboxyl cage silsesquioxane solution; In step 2, the amount of polycarboxyl cage silsesquioxane solution corresponding to each gram of leather is 1-9 mL; the volume ratio of polycarboxyl cage silsesquioxane solution to deionized water is 0.02-0.18:1; the mass ratio of pyrrole monomer to leather is 0.25-1.25:1, and the molar ratio of pyrrole monomer to ferric chloride is 1:4; In step 2, the stirring reaction temperature after adding pyrrole monomer is 0-4℃, and the reaction time is 1-2 h; In step 2, the ferric chloride solution is added at a speed of 1-3 drops / s.

2. The method of claim 1, wherein the leather-based friction nanogenerator having high output performance is prepared by the steps of: In step 1.1, the mass ratio of octavinyl cage silsesquioxane to tetrahydrofuran is 1:390-410, the concentration of solution B is 0.035-0.038 g / mL, the concentration of ammonium persulfate is 0.048-0.078 g / mL, the concentration of sodium bisulfite is 0.032-0.049 g / mL, and the concentration of methyl methacrylate is 0.12-0.18 g / mL.

3. The method of claim 1, wherein the leather-based friction nanogenerator having high output performance is prepared by the steps of: In step 1.2, the stirring reaction temperature after mixing solution A and solution B is 50-60℃, and the reaction time is 25-35 min.

4. The method of claim 1, wherein the leather-based tribo-nanogenerator having high output performance is prepared by the steps of: In step 1.2, the specific way of adding solution C is as follows: first, add 1 / 3 of solution C, stir at 50-60℃ for 25-35 min, then add 1 / 3 of solution C, stir at 50-60℃ for 25-35 min, finally add the remaining solution C, and stir at 50-60℃ for 200-230 min.

5. The method of claim 1, wherein the leather-based friction nanogenerator having high output performance is prepared by the steps of: The ultrasonic cleaning time is 10-30 min.