Flexible bone glue-based friction nanometer generator positive friction layer material and preparation method thereof

Abstract

The invention discloses a preparation method of a positive friction layer material of a flexible bone glue-based friction nano-generator, and belongs to the technical field of nano-energy, and the preparation method specifically comprises the following steps: preparing PILs; preparing a POSS polymer solution; preparing a POSS polymer modified bone glue composite solution; and preparing the POSS polymer modified bone glue composite film by adopting a solution pouring method. The invention further discloses a positive friction layer material of the flexible bone glue-based friction nanometer generator, and the problems that an existing bone glue-based positive friction layer material is insufficient in electron supply capacity and poor in mechanical property are solved.

Description

Technical Field

[0001] The present invention belongs to the field of nano energy technology, and specifically relates to a positive friction layer material of a flexible bone gelatin-based friction nanogenerator. The present invention also relates to a preparation method of the above-mentioned flexible bone gelatin-based friction nanogenerator positive friction layer material. Background Art

[0002] As a new type of energy capture device, the friction nanogenerator can convert tiny mechanical energy in the external environment into electrical energy through contact electrification and electrostatic induction coupling technology. It has the advantages of simple equipment, low cost, flexibility and integration, and has great application potential in the field of flexible self-powered sensing.

[0003] As an important component of the triboelectric nanogenerator, the positive friction layer has abundant electron-donating groups, such as alkyl, amino, and hydroxyl groups. During the contact and separation process with the negative friction layer, it can generate positive charges based on the contact electrification effect and provide electrons for the negative friction layer, thereby realizing the conversion of mechanical energy into electrical energy. However, traditional positive friction layer materials are mostly metal materials or synthetic polymer materials. As the concept of sustainable development has become popular, it is particularly important to develop degradable positive friction layer materials.

[0004] Bone glue is a thermal decomposition product of discarded livestock and poultry bones. It has excellent biocompatibility and biodegradability. Its molecular chain contains abundant amino electron-donating groups, which can be used as a positive friction layer material for triboelectric nanogenerators. However, the current bone glue-based positive friction layer materials have poor mechanical properties and are difficult to apply in flexible self-powered sensors. On the other hand, due to the insufficient content of electron-donating groups, the positive triboelectric properties need to be further improved. Summary of the invention

[0005] The purpose of the present invention is to provide a method for preparing a flexible gelatin-based friction nanogenerator positive friction layer material. The prepared flexible gelatin-based friction nanogenerator positive friction layer material solves the problems of insufficient electron supply capacity and poor mechanical properties of the current gelatin-based positive friction layer material.

[0006] Another object of the present invention is to provide the above-mentioned flexible bone gelatin-based friction nanogenerator positive friction layer material.

[0007] The technical solution adopted by the present invention is a method for preparing a positive friction layer material of a flexible bone gelatin-based friction nanogenerator, comprising the following steps: Step 1: Preparation of PILs; Step 2: preparing a POSS polymer solution; Step 3: preparing a POSS polymer-modified bone glue composite solution; Step 4: Prepare the POSS polymer modified bone glue composite film by solution casting method.

[0008] The present invention is also characterized in that: Step 1 specifically includes the following steps: Step 1.1: Weigh 1-vinylimidazole and dibromoalkane in a mass ratio of 1:2-5 and add them into a three-necked flask equipped with a condenser; Step 1.2: Add methanol to a three-necked flask and react in an oil bath at 70-90 °C for 8-14 h; the mass ratio of methanol to the total mass of 1-vinylimidazole and dibromoalkane is 2-10:1; Step 1.3: The solution obtained in step 1.2 was placed in a vacuum oven to dry to remove methanol, then washed with ethyl acetate for 3 to 5 times and continued to be vacuum dried to obtain PILs.

[0009] The dibromoalkane is any one of 1,2-dibromobutane, 1,6-dibromohexane, 1,8-dibromooctane, 1,10-dibromodecane, and 1,12-dibromododecane.

[0010] Step 2 specifically includes the following steps: Step 2.1: POSS-Vi is weighed and dispersed in a mixed solution of deionized water and tetrahydrofuran, and transferred into a three-necked flask equipped with a condenser, and stirred and dispersed at 200 r / min for 10 min at 25 °C; the mass ratio of POSS-Vi to the mixed solution of deionized water and tetrahydrofuran is 1:50-500, and the mass ratio of deionized water to tetrahydrofuran in the mixed solution of deionized water and tetrahydrofuran is 10-30:1; Step 2.2: Add a 0.5% photoinitiator solution to a three-necked flask, stir rapidly at 400 r / min for 10 min, irradiate with a UV lamp, and drop a mixed solution of PILs, amide monomers and AGE at a rate of 3-5 s / drop; after the addition is completed, continue irradiating with the UV lamp for 20 min and react for 2-5 h to obtain a POSS polymer solution; The mass ratio of PILs, amide monomers, and AGE in the mixed solution of PILs, amide monomers, and AGE is 1:1:1; The mass ratio of PILs to POSS-Vi was 3–40:1; The volume ratio of the photoinitiator solution to the mass ratio of the monomer is 0.5~2:1 mL / g; the mass of the monomer is the total mass of POSS-Vi, amide monomers, AGE, and PILs.

[0011] The photoinitiator is any one of α,α-dimethoxy-α-phenylacetophenone, α,α-dialkoxyacetophenone, and 2-hydroxy-2-methyl-1-phenyl-1-propanone; The amide monomer is any one of acrylamide, methacrylamide, dimethylacrylamide, N,N-methylacrylamide and N,N-methyleneacrylamide.

[0012] Step 3 specifically includes the following steps: Step 3.1: Weigh bone glue into deionized water, stir magnetically at 70-80 °C for 20-60 min until the bone glue is completely dissolved, to obtain a bone glue solution; the mass ratio of bone glue to deionized water is 1:4-30; Step 3.2: Add the POSS polymer solution into the gelatin solution and react for 3 to 6 hours to obtain a POSS polymer-modified gelatin composite solution; the mass ratio of the POSS polymer solution to the gelatin is 0.5 to 8:1.

[0013] Step 4 is as follows: 7-15 g of POSS polymer-modified bone glue composite solution was cast onto a polytetrafluoroethylene template by solution casting method, and then placed in a vacuum oven at 40-60 °C for 3-8 h to obtain a POSS polymer-modified bone glue composite film; the size of the POSS polymer-modified bone glue composite film was 5 cm×5 cm and the thickness was 0.1-0.5 mm.

[0014] Another technical solution adopted by the present invention is that the positive friction layer material of the flexible bone gelatin-based friction nanogenerator is prepared by the above method.

[0015] The beneficial effects of the present invention are: The present invention uses waste livestock and poultry bone extract gelatin as a substrate to prepare a POSS polymer modified gelatin composite film with excellent mechanical properties and positive triboelectricity. First, a POSS polymer containing an amide group, an imidazole cation, and an epoxy group is prepared by a free radical polymerization method; then, the gelatin is modified by the POSS polymer, and a POSS polymer modified gelatin composite film is obtained by a solution casting method. The tensile strength of the composite film is maintained at 5 MPa, and the elongation at break is increased to 190%; the composite film is used as a positive friction layer and the PDMS film is used as a negative friction layer to construct a friction nanogenerator, and the triboelectric output voltage is increased to 180V. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a flow chart of the preparation method of the positive friction layer material of the flexible bone gelatin-based friction nanogenerator of the present invention; Figure 2 is a graph of tensile strength and elongation at break of the positive friction layer material of the flexible bone gelatin-based triboelectric nanogenerator prepared in Example 1 of the present invention; Figure 3 This is a diagram of the triboelectric output voltage of a triboelectric nanogenerator constructed using the positive friction layer material of the flexible bone gelatin-based triboelectric nanogenerator prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0017] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0018] The method for preparing the positive friction layer material of the flexible gelatin-based friction nanogenerator of the present invention first designs and synthesizes a POSS polymer containing an amide group, an imidazolium cation, and an epoxy group; then the POSS polymer is blended with a gelatin solution to prepare a POSS polymer-modified gelatin composite film having excellent mechanical properties and positive triboelectric properties. The amide group and imidazolium cation in the POSS polymer are used to improve the electron donation ability of the gelatin; the Si-O-Si three-dimensional cage structure is used to enhance the charge capture ability of the gelatin; the ring-opening reaction between the epoxy group and the amino group on the BG molecular chain is used to insert the flexible long chain containing the ether group between the gelatin molecular chains to enhance the mechanical strength of the gelatin; in addition, the hydrogen bonding between the amide group, the imidazolium group and the hydroxyl group and the carboxyl group on the gelatin molecular chain is used to weaken the interaction between the gelatin molecular chains and improve the flexibility of the gelatin. The present invention is of great significance to the application of gelatin in the field of flexible self-powered sensing. Figure 1 As shown, the specific steps include: Step 1: Preparation of PILs.

[0019] Step 1.1: Weigh 1-vinylimidazole and dibromoalkane in a mass ratio of 1:2-5 and add them into a three-necked flask equipped with a condenser; wherein the dibromoalkane is any one of 1,2-dibromobutane, 1,6-dibromohexane, 1,8-dibromooctane, 1,10-dibromodecane, and 1,12-dibromododecane; Step 1.2: Add methanol (analytical grade) to a three-necked flask and react in an oil bath at 70-90 °C for 8-14 h; the mass ratio of methanol to the total mass of 1-vinylimidazole and dibromoalkane is 2-10:1; Step 1.3: The solution obtained in step 1.2 was placed in a vacuum oven to dry to remove methanol, then washed with ethyl acetate for 3 to 5 times and continued to be vacuum dried to obtain PILs.

[0020] Step 2: Preparation of POSS polymer solution.

[0021] Step 2.1: POSS-Vi is weighed and dispersed in a mixed solution of deionized water and tetrahydrofuran, and transferred into a three-necked flask equipped with a condenser, and stirred and dispersed at 200 r / min for 10 min at 25 °C; the mass ratio of POSS-Vi to the mixed solution of deionized water and tetrahydrofuran is 1:50-500, and the mass ratio of deionized water to tetrahydrofuran in the mixed solution of deionized water and tetrahydrofuran is 10-30:1; Step 2.2: Add a 0.5% photoinitiator solution to a three-necked flask, stir rapidly at 400 r / min for 10 min, irradiate with a UV lamp, and drop a mixed solution of PILs, amide monomers and AGE at a rate of 3-5 s / drop; after the addition is completed, continue irradiating with the UV lamp for 20 min and react for 2-5 h to obtain a POSS polymer solution; The amide monomer is any one of acrylamide, methacrylamide, dimethylacrylamide, N,N-methylacrylamide, and N,N-methyleneacrylamide. The mass ratio of PILs, amide monomers, and AGE in the mixed solution of PILs, amide monomers, and AGE is 1:1:1; The mass ratio of PILs to POSS-Vi was 3–40:1; The photoinitiator is any one of α,α-dimethoxy-α-phenylacetophenone, α,α-dialkoxyacetophenone, and 2-hydroxy-2-methyl-1-phenyl-1-propanone; the mass ratio of the volume of the photoinitiator solution to the monomer is 0.5~2:1 mL / g; the mass of the monomer is the total mass of POSS-Vi, amide monomers, AGE, and PILs.

[0022] Step 3: Prepare the POSS polymer-modified bone glue composite solution.

[0023] Step 3.1: Weigh bone glue into deionized water, stir magnetically at 70-80 °C for 20-60 min until the bone glue is completely dissolved, to obtain a bone glue solution; the mass ratio of bone glue to deionized water is 1:4-30; Step 3.2: Add the POSS polymer solution into the gelatin solution and react for 3 to 6 hours to obtain a POSS polymer-modified gelatin composite solution; the mass ratio of the POSS polymer solution to the gelatin is 0.5 to 8:1.

[0024] Step 4: Prepare the POSS polymer modified bone glue composite film by solution casting method.

[0025] 7-15 g of POSS polymer-modified bone glue composite solution was cast onto a polytetrafluoroethylene template by solution casting method, and then placed in a vacuum oven at 40-60 °C for 3-8 h to obtain a POSS polymer-modified bone glue composite film; the size of the POSS polymer-modified bone glue composite film was 5 cm×5 cm and the thickness was 0.1-0.5 mm.

[0026] The present invention uses waste livestock and poultry bone extract gelatin as a substrate to prepare a POSS polymer modified gelatin composite film with excellent mechanical properties and positive triboelectricity. First, a POSS polymer containing amide groups, imidazole cations and epoxy groups is prepared by free radical polymerization; then, the gelatin is modified by the POSS polymer, and a POSS polymer modified gelatin composite film is obtained by a solution casting method. The tensile strength of the composite film is maintained at 5 MPa, and the elongation at break is increased from 30% to 190%; the composite film is used as a positive friction layer and the PDMS film is used as a negative friction layer to construct a friction nanogenerator, and the triboelectric output voltage is increased from 80 V to 180 V.

[0027] Example 1 This embodiment provides a method for preparing a positive friction layer material of a flexible bone gelatin-based triboelectric nanogenerator, which specifically comprises the following steps: Step 1: Preparation of PILs.

[0028] Step 1.1: Weigh 2.2687 g of 1-vinylimidazole and 5.0661 g of 1,2-dibromobutane into a three-necked flask equipped with a condenser; Step 1.2: Add 20 g methanol (analytical grade) into a three-necked flask and react in an oil bath at 70 °C for 8 h; Step 1.3: The solution obtained in step 1.2 was placed in a vacuum oven to dry to remove methanol, then washed with ethyl acetate three times and continued to be vacuum dried to obtain PILs.

[0029] Step 2: Preparation of POSS polymer solution.

[0030] Step 2.1: Weigh 0.06 g of POSS-Vi and disperse it in a mixed solution prepared by 10 g of deionized water and 1 g of tetrahydrofuran, transfer it into a three-necked flask equipped with a condenser, and stir and disperse it at 200 r / min at 25 °C for 10 min; Step 2.2: Prepare a 0.5% α,α-dimethoxy-α-phenylacetophenone solution, add 3 mL into a three-necked flask, and stir rapidly at 400 r / min for 10 min; irradiate with ultraviolet light, and add a mixed solution prepared by 0.98 g PILs, 0.98 g acrylamide and 0.98 g AGE at a rate of 3 s / drop; after the addition is completed, continue to irradiate with ultraviolet light for 20 min and react for 3 h to obtain a POSS polymer solution.

[0031] Step 3: Prepare the POSS polymer-modified bone glue composite solution.

[0032] Step 3.1: Weigh 0.35 g of bone glue into 9.65 g of deionized water, and stir magnetically at 70 °C for 30 min until the bone glue is completely dissolved to obtain a bone glue solution; Step 3.2: Take 0.4667 g of POSS polymer solution and add it into the gelatin solution to react for 3 h to obtain a POSS polymer-modified gelatin composite solution.

[0033] Step 4: Prepare the POSS polymer modified bone glue composite film by solution casting method.

[0034] 8.5 g of POSS polymer-modified bone glue composite solution was cast onto a polytetrafluoroethylene template by solution casting method, and then placed in a vacuum oven at 40 °C for 5 h to obtain a POSS polymer-modified bone glue composite film; the size of the POSS polymer-modified bone glue composite film was 5 cm×5 cm and the thickness was 0.18 mm.

[0035] Example 2 This embodiment provides a method for preparing a positive friction layer material of a flexible bone gelatin-based triboelectric nanogenerator, which specifically comprises the following steps: Step 1: Preparation of PILs.

[0036] Step 1.1: weigh 6.8060 g of 1-vinylimidazole and 15.1982 g of 1,6-dibromohexane into a three-necked flask equipped with a condenser; Step 1.2: Add 50 g methanol (analytical grade) into a three-necked flask and react in an oil bath at 80 °C for 10 h; Step 1.3: The solution obtained in step 1.2 was placed in a vacuum oven to dry to remove methanol, then washed with ethyl acetate 4 times and continued to be vacuum dried to obtain PILs.

[0037] Step 2: Preparation of POSS polymer solution.

[0038] Step 2.1: Weigh 0.2 g of POSS-Vi and disperse it in a mixed solution prepared by 44.6667 g of deionized water and 2 g of tetrahydrofuran, transfer it into a three-necked flask equipped with a condenser, and stir and disperse it at 25 °C and 200 r / min for 10 min; Step 2.2: Prepare 0.5% α,α-dialkoxyacetophenone solution, add 5 mL into a three-necked flask, and stir rapidly at 400 r / min for 10 min; irradiate with ultraviolet light, and add a mixed solution prepared by 3.2667 g PILs, 3.2667 g dimethylacrylamide and 3.2667 g AGE at a rate of 4 s / drop; after the addition is completed, continue to irradiate with ultraviolet light for 20 min and react for 2 h to obtain a POSS polymer solution.

[0039] Step 3: Prepare the POSS polymer-modified bone glue composite solution.

[0040] Step 3.1: Weigh 2 g of bone glue into 38 g of deionized water, and stir with magnetic force at 75 °C for 30 min until the bone glue is completely dissolved to obtain a bone glue solution; Step 3.2: Take 15 g of POSS polymer solution and add it into the gelatin solution to react for 4 h to obtain a POSS polymer-modified gelatin composite solution.

[0041] Step 4: Prepare the POSS polymer modified bone glue composite film by solution casting method.

[0042] 10 g of POSS polymer modified bone glue composite solution was cast onto a polytetrafluoroethylene template by solution casting method, and then the POSS polymer modified bone glue composite film was obtained in a vacuum oven at 50 °C for 8 h; the size of the POSS polymer modified bone glue composite film was 5 cm×5 cm and the thickness was 0.25 mm.

[0043] Example 3 This embodiment provides a method for preparing a positive friction layer material of a flexible bone gelatin-based triboelectric nanogenerator, which specifically comprises the following steps: Step 1: Preparation of PILs.

[0044] Step 1.1: Weigh 10.418 g of 1-vinylimidazole and 36.5946 g of 1,12-dibromododecane into a three-necked flask equipped with a condenser; Step 1.2: Add 300 g methanol (analytical grade) into a three-necked flask and react in an oil bath at 85 °C for 10 h; Step 1.3: The solution obtained in step 1.2 was placed in a vacuum oven to dry to remove methanol, then washed with ethyl acetate three times and continued to be vacuum dried to obtain PILs.

[0045] Step 2: Preparation of POSS polymer solution.

[0046] Step 2.1: Weigh 2 g of POSS-Vi and disperse it in a mixed solution prepared by 120 g of deionized water and 5 g of tetrahydrofuran, transfer it into a three-necked flask equipped with a condenser, and stir and disperse it at 25 °C and 200 r / min for 10 min; Step 2.2: Prepare 0.5% α,α-dialkoxyacetophenone solution, add 20 mL into a three-necked flask, and stir rapidly at 400 r / min for 10 min; irradiate with UV light, and add a mixed solution prepared by 6 g PILs, 6 g dimethylacrylamide and 6 g AGE at a rate of 4 s / drop; after the addition is completed, continue to irradiate with UV light for 20 min and react for 2 h to obtain a POSS polymer solution.

[0047] Step 3: Prepare the POSS polymer-modified bone glue composite solution.

[0048] Step 3.1: Weigh 10 g of bone glue into 90 g of deionized water, stir magnetically at 75 °C for 30 min until the bone glue is completely dissolved to obtain a bone glue solution; Step 3.2: Take 46.6667 g of POSS polymer solution and add it into the gelatin solution to react for 4 h to obtain a POSS polymer-modified gelatin composite solution.

[0049] Step 4: Prepare the POSS polymer modified bone glue composite film by solution casting method.

[0050] 9 g of POSS polymer-modified bone glue composite solution was cast onto a polytetrafluoroethylene template by solution casting method, and then the POSS polymer-modified bone glue composite film was obtained in a vacuum oven at 60 °C for 6 h; the size of the POSS polymer-modified bone glue composite film was 5 cm×5 cm and the thickness was 0.3 mm.

[0051] Example 4 This embodiment provides a method for preparing a positive friction layer material of a flexible bone gelatin-based triboelectric nanogenerator, which specifically comprises the following steps: Step 1: Preparation of PILs.

[0052] Step 1.1: Weigh 1.1343 g of 1-vinylimidazole and 4.5373 g of 1,8-dibromooctane into a three-necked flask equipped with a condenser; Step 1.2: Add 40 g methanol (analytical grade) into a three-necked flask and react in an oil bath at 85 °C for 12 h; Step 1.3: The solution obtained in step 1.2 was placed in a vacuum oven to dry to remove methanol, then washed with ethyl acetate 4 times and continued to be vacuum dried to obtain PILs.

[0053] Step 2: Preparation of POSS polymer solution.

[0054] Step 2.1: Weigh 0.5 g of POSS-Vi and disperse it in a mixed solution prepared by 60 g of deionized water and 2 g of tetrahydrofuran, transfer it into a three-necked flask equipped with a condenser, and stir and disperse it at 25 °C and 200 r / min for 10 min; Step 2.2: Prepare a 0.5% α,α-dimethoxy-α-phenylacetophenone solution, add 10.5 mL into a three-necked flask, and stir rapidly at 400 r / min for 10 min; irradiate with ultraviolet light, and add a mixed solution prepared by 3.1667 g PILs, 3.1667 g methacrylamide and 3.1667 g AGE at a rate of 3 s / drop; after the addition is completed, continue to irradiate with ultraviolet light for 20 min and react for 5 h to obtain a POSS polymer solution.

[0055] Step 3: Prepare the POSS polymer-modified bone glue composite solution.

[0056] Step 3.1: Weigh 6 g of bone glue into 85 g of deionized water, and stir magnetically at 75 °C for 60 min until the bone glue is completely dissolved to obtain a bone glue solution; Step 3.2: Take 12 g of POSS polymer solution and add it into the gelatin solution to react for 3 h to obtain a POSS polymer-modified gelatin composite solution.

[0057] Step 4: Prepare the POSS polymer modified bone glue composite film by solution casting method.

[0058] 10 g of POSS polymer modified bone glue composite solution was cast onto a polytetrafluoroethylene template by solution casting method, and then the POSS polymer modified bone glue composite film was obtained in a vacuum oven at 45 °C for 7 h; the size of the POSS polymer modified bone glue composite film was 5 cm×5 cm and the thickness was 0.285 mm.

[0059] Example 5 This embodiment provides a method for preparing a positive friction layer material of a flexible bone gelatin-based triboelectric nanogenerator, which specifically comprises the following steps: Step 1: Preparation of PILs.

[0060] Step 1.1: weigh 5.6845 g of 1-vinylimidazole and 17.0535 g of 1,8-dibromooctane into a three-necked flask equipped with a condenser; Step 1.2: Add 100 g methanol (analytical grade) into a three-necked flask and react in an oil bath at 85 °C for 13 h; Step 1.3: The solution obtained in step 1.2 was placed in a vacuum oven to dry to remove methanol, then washed with ethyl acetate three times and continued to be vacuum dried to obtain PILs.

[0061] Step 2: Preparation of POSS polymer solution.

[0062] Step 2.1: Weigh 0.08 g of POSS-Vi and disperse it in a mixed solution prepared by 25 g of deionized water and 1 g of tetrahydrofuran, transfer it into a three-necked flask equipped with a condenser, and stir and disperse it at 200 r / min at 25 °C for 10 min; Step 2.2: Prepare 0.5% 2-hydroxy-2-methyl-1-phenyl-1-propanone solution, add 4 mL into a three-necked flask, and stir rapidly at 400 r / min for 10 min; irradiate with ultraviolet light, and add a mixed solution prepared by 1.64 g PILs, 1.64 g acrylamide and 1.64 g AGE at a rate of 4 s / drop; after the addition is completed, continue to irradiate with ultraviolet light for 20 min and react for 4 h to obtain a POSS polymer solution.

[0063] Step 3: Prepare the POSS polymer-modified bone glue composite solution.

[0064] Step 3.1: Weigh 10 g of bone glue into 40 g of deionized water, stir magnetically at 75 °C for 60 min until the bone glue is completely dissolved to obtain a bone glue solution; Step 3.2: 16.6667 g of POSS polymer solution was added to the gelatin solution and reacted for 2 h to obtain a POSS polymer-modified gelatin composite solution.

[0065] Step 4: Prepare the POSS polymer modified bone glue composite film by solution casting method.

[0066] 12 g of POSS polymer-modified bone glue composite solution was cast onto a polytetrafluoroethylene template by solution casting method, and then the POSS polymer-modified bone glue composite film was obtained in a vacuum oven at 40 °C for 7 h; the size of the POSS polymer-modified bone glue composite film was 5 cm×5 cm and the thickness was 0.45 mm.

[0067] Example 6 This embodiment provides a method for preparing a positive friction layer material of a flexible bone gelatin-based triboelectric nanogenerator, which specifically comprises the following steps: Step 1: Preparation of PILs.

[0068] Step 1.1: Weigh 10.2090 g of 1-vinylimidazole and 30.627 g of 1,8-dibromooctane into a three-necked flask equipped with a condenser; Step 1.2: Add 150 g methanol (analytical grade) into a three-necked flask and react in an oil bath at 85 °C for 14 h; Step 1.3: The solution obtained in step 1.2 was placed in a vacuum oven to dry to remove methanol, then washed with ethyl acetate 4 times and continued to be vacuum dried to obtain PILs.

[0069] Step 2: Preparation of POSS polymer solution.

[0070] Step 2.1: Weigh 2.5 g of POSS-Vi and disperse it in a mixed solution prepared by 190 g of deionized water and 8 g of tetrahydrofuran, transfer it into a three-necked flask equipped with a condenser, and stir and disperse it at 200 r / min at 25 °C for 10 min; Step 2.2: Prepare a 0.5% α,α-dimethoxy-α-phenylacetophenone solution, add 18 mL into a three-necked flask, and stir rapidly at 400 r / min for 10 min; irradiate with ultraviolet light, and add a mixed solution prepared by 9.1667 g PILs, 9.1667 g methacrylamide and 9.1667 g AGE at a rate of 3 s / drop; after the addition is completed, continue to irradiate with ultraviolet light for 20 min and react for 5 h to obtain a POSS polymer solution.

[0071] Step 3: Prepare the POSS polymer-modified bone glue composite solution.

[0072] Step 3.1: Weigh 8 g of bone glue into 150 g of deionized water, and stir with magnetic force at 80 °C for 30 min until the bone glue is completely dissolved to obtain a bone glue solution; Step 3.2: Take 21.3333 g of POSS polymer solution and add it into the gelatin solution to react for 6 h to obtain a POSS polymer-modified gelatin composite solution.

[0073] Step 4: Prepare the POSS polymer modified bone glue composite film by solution casting method.

[0074] 15 g of POSS polymer-modified bone glue composite solution was cast onto a polytetrafluoroethylene template by solution casting method, and then the POSS polymer-modified bone glue composite film was obtained in a vacuum oven at 50 °C for 5 h; the size of the POSS polymer-modified bone glue composite film was 5 cm×5 cm and the thickness was 0.19 mm.

[0075] Comparative Example Step 1: Weigh 0.35 g of bone glue into 9.65 g of deionized water, and stir magnetically at 70 °C for 30 min until the bone glue is completely dissolved to obtain a bone glue solution; Step 2: Take 8.5 g of gelatin solution and cast it onto a polytetrafluoroethylene template by solution casting method, and place it in a vacuum oven at 40 °C for 5 h to obtain a gelatin film; the size of the gelatin film is 5 cm × 5 cm and the thickness is 0.18 mm.

[0076] The POSS polymer modified bone glue composite film prepared in Example 1 and the bone glue film prepared in the comparative example were subjected to tensile tests. The results are as follows: Figure 2 As shown in the figure, the tensile strength of the POSS polymer modified bone glue composite film is about 0.5MPa higher than that of the bone glue film, and the elongation at break is significantly improved, about 120%. At the same time, the two films were used to construct a triboelectric nanogenerator, and the triboelectric output voltage was as follows Figure 3 As shown, the output voltage of the friction nanogenerator constructed using the POSS polymer modified bone glue composite film prepared by the present invention is significantly better than the output voltage of the friction nanogenerator constructed using the bone glue film. The above experiments show that the POSS polymer modified bone glue composite film prepared by the present invention has excellent mechanical properties and electron donation ability.

Claims

1. A method for preparing a positive friction layer material of a flexible bone gelatin-based friction nanogenerator, characterized in that: The steps include: Step 1: Preparation of PILs; Step 2: preparing a POSS polymer solution; Step 3: preparing a POSS polymer-modified bone glue composite solution; Step 4: Prepare the POSS polymer modified bone glue composite film by solution casting method.

2. The method for preparing the positive friction layer material of the flexible bone gelatin-based triboelectric nanogenerator according to claim 1, characterized in that: Step 1 specifically includes the following steps: Step 1.1: Weigh 1-vinylimidazole and dibromoalkane in a mass ratio of 1:2-5 and add them into a three-necked flask equipped with a condenser; Step 1.2: Add methanol to a three-necked flask and react in an oil bath at 70-90° C. for 8-14 h; the mass ratio of the methanol to the total mass of 1-vinylimidazole and dibromoalkane is 2-10:1; Step 1.3: The solution obtained in step 1.2 was placed in a vacuum oven to dry to remove methanol, then washed with ethyl acetate for 3 to 5 times and continued to be vacuum dried to obtain PILs.

3. The method for preparing the positive friction layer material of the flexible bone gelatin-based triboelectric nanogenerator according to claim 2, characterized in that: The dibromoalkane is any one of 1,2-dibromobutane, 1,6-dibromohexane, 1,8-dibromooctane, 1,10-dibromodecane and 1,12-dibromododecane.

4. The method for preparing the positive friction layer material of the flexible bone gelatin-based triboelectric nanogenerator according to claim 3, characterized in that: Step 2 specifically includes the following steps: Step 2.1: POSS-Vi is weighed and dispersed in a mixed solution of deionized water and tetrahydrofuran, and transferred into a three-necked flask equipped with a condenser, and stirred and dispersed at 200 r / min for 10 min at 25°C; the mass ratio of the POSS-Vi to the mixed solution of deionized water and tetrahydrofuran is 1:50-500, and the mass ratio of deionized water to tetrahydrofuran in the mixed solution of deionized water and tetrahydrofuran is 10-30:1; Step 2.2: Add a 0.5% photoinitiator solution to a three-necked flask, stir rapidly at 400 r / min for 10 min, irradiate with a UV lamp, and drop a mixed solution of PILs, amide monomers and AGE at a rate of 3-5 s / drop; after the addition is completed, continue irradiating with the UV lamp for 20 min and react for 2-5 h to obtain a POSS polymer solution; The mass ratio of PILs, amide monomers and AGE in the mixed solution of PILs, amide monomers and AGE is 1:1:1; The mass ratio of the PILs to POSS-Vi is 3-40:1; The volume ratio of the photoinitiator solution to the mass ratio of the monomer is 0.5-2:1 mL / g; the mass of the monomer is the total mass of POSS-Vi, amide monomers, AGE, and PILs.

5. The method for preparing the positive friction layer material of the flexible bone gelatin-based triboelectric nanogenerator according to claim 4, characterized in that: The photoinitiator is any one of α,α-dimethoxy-α-phenylacetophenone, α,α-dialkoxyacetophenone, and 2-hydroxy-2-methyl-1-phenyl-1-propanone; The amide monomer is any one of acrylamide, methacrylamide, dimethylacrylamide, N,N-methylacrylamide and N,N-methyleneacrylamide.

6. The method for preparing the positive friction layer material of the flexible bone gelatin-based triboelectric nanogenerator according to claim 5, characterized in that: Step 3 specifically includes the following steps: Step 3.1: Weigh bone glue into deionized water, and stir magnetically at 70-80°C for 20-60 min until the bone glue is completely dissolved to obtain a bone glue solution; the mass ratio of the bone glue to deionized water is 1:4-30; Step 3.2: adding the POSS polymer solution to the gelatin solution and reacting for 3-6 h to obtain a POSS polymer-modified gelatin composite solution; The mass ratio of the POSS polymer solution to the bone glue is 0.5-8:

1.

7. The method for preparing the positive friction layer material of the flexible bone gelatin-based triboelectric nanogenerator according to claim 6, characterized in that: Step 4 is as follows: 7-15 g of POSS polymer-modified bone glue composite solution was cast onto a polytetrafluoroethylene template by a solution casting method, and then placed in a vacuum oven at 40-60 °C for 3-8 h to obtain a POSS polymer-modified bone glue composite film; the POSS polymer-modified bone glue composite film had a size of 5 cm×5 cm and a thickness of 0.1-0.5 mm.

8. A flexible bone gelatin-based friction nanogenerator positive friction layer material, characterized in that: The method according to claim 7 is used for preparation.

Images