A light-driven morphing photoactive film, a preparation method thereof and application thereof in a biomimetic actuator and a photoelectric conversion triboelectric nanogenerator

Abstract

The application discloses a light-driven film capable of deforming in response to light, a preparation method of the light-driven film and application of the light-driven film in a biomimetic driver and a photoelectric conversion friction nanogenerator, and belongs to the technical field of flexible driver materials. The preparation method comprises the following steps: (1) preparing a black pigment solution; (2) preparing a Nafion-black pigment solution; (3) preparing a Nafion-black pigment film; and (4) preparing a Nafion / black pigment / polyethylene light-driven film. The light-driven film is made of Nafion / black pigment / polyethylene materials, when light irradiation occurs, the Nafion / black pigment / polyethylene materials are automatically opened in response to light, and with the increase of light intensity, the opening angle of the Nafion / black pigment / polyethylene materials is increased. When there is no light irradiation, the Nafion / black pigment / polyethylene materials are automatically closed and restored to the state before light irradiation, so that the purpose of remotely controlling the driver by using a light source is achieved, and the light-driven film has the advantages of simple structure and convenient driving.

Description

Technical Field

[0001] This invention relates to the field of flexible actuator materials technology, specifically to a photo-responsive deformable photoelectric drive film, its preparation method, and its application in biomimetic actuators and photoelectric conversion triboelectric nanogenerators. Background Technology

[0002] Flexible smart materials enable the rapid conversion of light energy into mechanical energy. Flexible robots made from these materials mimic the movements of plants and animals, allowing for large deformations and continuous, high-degree-of-freedom motion in complex natural environments. They can perform various movements such as climbing, jumping, and curling. Unlike traditional rigid robots, flexible robots offer advantages such as simple structure, lightweight design, high degrees of freedom, good environmental adaptability, and low operating noise, and are currently attracting widespread attention in fields such as national defense and biomedical devices.

[0003] Despite the fruitful results achieved in the research on driving flexible smart materials, there is still much room for exploration and progress in the research on biomimetic driving and continuous light stimulation.

[0004] Therefore, there is a need to provide a driver that can achieve various forms of biomimetic motion and realize a higher-power photoelectric conversion triboelectric nanogenerator under light stimulation.

[0005] Chinese patent application CN108484951A discloses a photothermal responsive material and a method for fabricating a photothermal driven robot, as well as its applications. Specifically, it involves introducing a composite film of graphene oxide and gold nanorods onto a polymethyl methacrylate (PMMA) film. This resulting bilayer film serves as the raw material for the robot. A commercially available optical disc laser scanning modification method is used to modify the upper composite film, resulting in a patterned robot structure. During scanning, the laser photoreduces the photo-driver regions within the robot structure, giving these regions of the composite film both high absorbance and high thermal conductivity. Together with the underlying PMMA film, this forms a highly efficient photo-driver assembly. When the robot is driven by a light source, the thermal expansion coefficient of the composite film in the reduced photo-driver regions is much smaller than that of the PMMA film, causing the photo-driver assembly to rapidly bend towards the composite film, thereby driving the robot's deformation or movement. However, this patent does not involve Nafion / black pigment / polyethylene materials and has relatively low photoelectric conversion efficiency.

[0006] Chinese patent application CN112853758A discloses a fast photothermal response shape memory actuator, its fabrication method, and its applications. The substrate is a flexible substrate fiber membrane with micro / nanofiber structure and shape memory function. Cellulose nanocrystals and conductive two-dimensional MXene material are deposited on the flexible substrate fiber membrane. The shape memory actuator of this invention has a fast photothermal response speed of 80–140 mW / cm². 2 Under near-infrared stimulation, the surface temperature of the shape memory actuator can rapidly reach over 80°C within 20 seconds. However, this patent does not involve Nafion / black pigment / polyethylene materials, and its photoelectric conversion efficiency is relatively low. Summary of the Invention

[0007] The technical problem to be solved by this invention is how to provide a light-driven film that can achieve functions such as automatic winding, unwinding, and climbing through remote light adjustment, as well as improve the performance of photoelectric conversion triboelectric nanogenerators, and is simple to prepare, has a short manufacturing process, and low material cost.

[0008] The present invention solves the above-mentioned technical problems through the following technical means:

[0009] The first aspect of this invention provides a method for preparing a photosensitive, deformable optical drive film, comprising the following steps:

[0010] (1) Preparation of black pigment solution: Grind the black pigment particles into powder, then add deionized water and mix thoroughly;

[0011] (2) Preparation of Nafion-black pigment solution: Nafion solution and N,N-dimethylacetamide (DMAC) solution are added to the black pigment solution in step (1), and the mixture is then ultrasonically treated to obtain Nafion-black pigment solution. The Nafion-black pigment solution is then vacuum-treated to remove internal gas impurities.

[0012] Note: The Nafion solution used is a perfluorosulfonic acid polymer solution.

[0013] (3) Preparation of Nafion-black pigment film: The Nafion-black pigment solution prepared in step (2) is dropped onto a glass slide, then heated and dried, and the Nafion-black pigment film is peeled off from the glass slide;

[0014] (4) Preparation of Nafion / black pigment / polyethylene optical drive film: Unfold and lay out a single-sided adhesive polyethylene tape, and then attach the Nafion-black pigment film to the polyethylene tape to obtain the optical drive film.

[0015] Beneficial effects: The optical drive film of this invention is made of Nafion / black pigment / polyethylene material. When illuminated by light, the Nafion / black pigment / polyethylene material automatically opens due to photosensitive properties, and the opening angle increases with the intensity of the light. When there is no light, the Nafion / black pigment / polyethylene material automatically closes and returns to its state before the light exposure. This achieves the goal of remotely controlling the driver using a light source, while also offering the advantages of simple structure and convenient operation.

[0016] Preferably, the ratio of the mass of black pigment to the volume of deionized water in step (1) is (0.01-0.1)g:(0.5-2)mL, more preferably 0.05g:1mL.

[0017] Preferably, the black pigment material is one or a combination of aniline black, insulating carbon black, and copper chromium black.

[0018] Preferably, the grinding device in step (1) is a mortar and pestle, and the grinding time is 5-15 min, more preferably 10 min.

[0019] Preferably, the mixing device in step (1) is a vortex mixer, and the mixing time is 10-20 min, more preferably 15 min.

[0020] Preferably, the mass ratio of Nafion to DMAC in step (2) is (1-5):(0.1-1), and more preferably, the mass ratio is 3:0.5.

[0021] Preferably, the ultrasonic power in step (2) is 300W and the ultrasonic time is 20-40min, more preferably 30min.

[0022] Preferably, the vacuum extraction time in step (2) is 5-15 min, more preferably 10 min.

[0023] Preferably, the glass sheet in step (3) has a size of 25×75mm.

[0024] Preferably, the Nafion-black pigment solution in step (3) is 2 mL.

[0025] Preferably, the temperature of the vacuum drying oven in step (3) is set to 30-80℃ and the heating time is 2-6h.

[0026] Preferably, the temperature of the vacuum drying oven in step (3) is set to 50°C and the heating time is 4 hours.

[0027] Preferably, in step (4), the Nafion-black pigment film is attached to the polyethylene tape along the length of the polyethylene tape, and then the two ends are glued together with tape to obtain the optical drive film for triboelectric nanogenerator.

[0028] Furthermore, in step (4), the polyethylene tape is first stretched along its length and then laid flat. Then, the Nafion black pigment film is attached to the polyethylene tape along its length to obtain the optical drive film for bionic drive.

[0029] Beneficial effects: Because polyethylene tape is anisotropic along its length, when preparing Nafion / aniline black / polyethylene materials, it is necessary to attach a Nafion-black pigment film along the length of the tape.

[0030] Furthermore, the polyethylene tape thickness in step (4) is 30 μm.

[0031] Furthermore, the prestress applied to the polyethylene tape in step (4) is to stretch its length by 10 mm.

[0032] Furthermore, in step (4), the thickness of the optical drive film is 60 μm, and the thickness ratio of the polyethylene tape to the Nafion black pigment film is 1:1.

[0033] A second aspect of the present invention provides a photodrive film prepared using the above-described preparation method.

[0034] A third aspect of the present invention proposes the application of the photoelectric drive film prepared by the above-described method in biomimetic actuators and photoelectric conversion triboelectric nanogenerators.

[0035] The advantages of this invention are:

[0036] 1. The optical drive film of the present invention is made of Nafion / black pigment / polyethylene material. When illuminated by light, the Nafion / black pigment / polyethylene material automatically opens due to photosensitive properties, and the opening angle of the Nafion / black pigment / polyethylene material increases with the increase of light intensity. When there is no light, the Nafion / black pigment / polyethylene material automatically closes and returns to its state before the light exposure.

[0037] 2. This invention utilizes the photothermal effect of black pigment to enhance the sensitivity of Nafion / black pigment / polyethylene material to light intensity, enabling the optical drive film to open under light source illumination and close when there is no light source illumination. Moreover, the opening angle increases with the increase of light intensity, achieving adjustable drive. This not only achieves the purpose of remotely controlling the driver using a light source, but also has the advantages of simple structure and convenient drive.

[0038] 3. This invention utilizes non-conductive black pigment to make it easier for electrons to accumulate on the surface of the actuator, thereby increasing the output voltage of the triboelectric nanogenerator.

[0039] 4. The photoelectric drive film of the present invention can enable the bionic artificial actuator to achieve functions such as automatic winding, unwinding, and climbing through remote light adjustment, as well as improve the performance of photoelectric conversion triboelectric nanogenerator. It is simple to prepare, has a short manufacturing process, and low material cost. Attached Figure Description

[0040] Figure 1 This is a schematic diagram of the preparation of the optical drive film in Example 1 of this application.

[0041] Figure 2 This is a light test diagram of the optical drive film in Embodiment 1 of this application.

[0042] Figure 3 This is a graph showing the light drive response bending angle performance of the optical drive film in Embodiment 1 of this application.

[0043] Figure 4 This is an optical photograph of the bionic actuator climbing a tree branch at a high altitude, as shown in Embodiment 1 of this application.

[0044] Figure 5 An optical photograph of the bionic actuator unwinding in Embodiment 1 of this application.

[0045] Figure 6 This is a schematic diagram of the preparation of the optical drive film in Example 2 of this application.

[0046] Figure 7 This is an optical photograph of the triboelectric nanogenerator of Example 2 of this application.

[0047] Explanation of reference numerals in the attached drawings: 1. Nafion-aniline black film; 2. Glass sheet with dimensions of 25×75mm; 3. Polyethylene tape. Detailed Implementation

[0048] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0049] Unless otherwise specified, all test materials and reagents used in the following examples are commercially available.

[0050] Unless otherwise specified in the embodiments, the techniques or conditions described in the literature in this field or in accordance with the product manual may be followed.

[0051] Example 1:

[0052] The fabrication of the optical drive film and its application in a bionic actuator include the following steps:

[0053] (1) Preparation of black pigment solution: Add 0.05g of aniline black particles to a mortar and grind for 10min to make it into powder. Then add the aniline black powder to a centrifuge tube and add 1mL of deionized water. Mix well with a vortex mixer for 15min.

[0054] (2) Preparation of Nafion-aniline black solution: Add 3g Nafion solution and 0.5g DMAC solution to aniline black solution, then sonicate the mixture in an ice bath at 300W for 30min to obtain Nafion-aniline black solution, which is fully dispersed. Then, vacuum the Nafion-aniline black solution for 10min to remove internal gas impurities.

[0055] (3) Preparation of Nafion-aniline black film: Using a pipette, 2 mL of the treated Nafion-aniline black solution was dropped onto a 25×75 mm glass slide, and then heated at 50 °C for 4 h in a vacuum drying oven. After drying, the glass slide with Nafion-aniline black was immersed in deionized water for 10 s, and the film (30 μm thick) could be automatically peeled off from the glass slide.

[0056] (4) Preparation of Nafion / aniline black / polyethylene optical drive film: stretch a single-sided adhesive polyethylene tape 10 mm along its length and then lay it flat (the tape thickness is 30 μm). Then attach the Nafion-aniline black film to the polyethylene and cut it into 5×60 mm pieces to obtain the rolled optical drive film.

[0057] The optical drive film was used as an optical drive to test its response to bending angle, climbing, and winding capabilities. Figure 3-5 .

[0058] Figure 1 This is a schematic diagram of the preparation of the optical drive film in Example 1 of this application.

[0059] Figure 2 This is a light test diagram of the optical drive film in Embodiment 1 of this application.

[0060] Figure 3 This is a graph showing the light drive response bending angle performance of the optical drive film in Embodiment 1 of this application.

[0061] Figure 4This is an optical photograph of the optical drive film in Embodiment 1 of this application, which acts as a bionic actuator to climb a tree branch high up.

[0062] Figure 5 An optical photograph showing the optical drive film in Embodiment 1 of this application unwinding as a bionic actuator.

[0063] Example 2:

[0064] The preparation of the optical drive film and its application in photoelectric conversion triboelectric nanogenerators include the following steps:

[0065] (1) Preparation of black pigment solution: Add 0.05g of aniline black particles to a mortar and grind for 10min to make it into powder. Then add the aniline black powder to a centrifuge tube and add 1mL of deionized water. Mix well with a vortex mixer for 15min.

[0066] (2) Preparation of Nafion-aniline black solution: Add 3g Nafion solution and 0.5g DMAC solution to aniline black solution, then sonicate the mixture in an ice bath at 300W for 30min to obtain Nafion-aniline black solution, which is fully dispersed. Then, vacuum the Nafion-aniline black solution for 10min to remove internal gas impurities.

[0067] (3) Preparation of Nafion-aniline black film: Using a pipette, 2 mL of the treated Nafion-aniline black solution was dropped onto a 25×75 mm glass slide, and then heated at 50 °C for 4 h in a vacuum drying oven. After drying, the glass slide with Nafion-aniline black was immersed in deionized water for 10 s, and the film (30 μm thick) could be automatically peeled off from the glass slide.

[0068] (4) Preparation of Nafion / aniline black / polyethylene optical drive film: unfold and lay the single-sided adhesive polyethylene flat, then attach the Nafion-aniline black film to the polyethylene and cut it into 10×70mm pieces. Then use polyethylene tape to stick the two ends together to obtain the optical drive film for photoelectric conversion triboelectric nanogenerator.

[0069] (5) Constructing the TENG platform: Cover the glass slide with two 40mm×40mm aluminum foils as electrode layers, and then cover them with a layer of Kapton tape as an insulating layer. Lead out copper wires directly between the aluminum foil electrode layers and the Kapton tape layer to transfer charge. Finally, place the ring-shaped Nafion / aniline black / polyethylene optical drive film on the constructed platform, apply light, and the optical drive film will move left and right to generate current.

[0070] Figure 6 This is a schematic diagram of the preparation of the optical drive film in Example 2 of this application.

[0071] Figure 7 An optical photograph of the optical drive film as a triboelectric nanogenerator in Embodiment 2 of this application.

[0072] Example 3:

[0073] A method for preparing a photosensitive deformable optical drive film includes the following steps:

[0074] (1) Preparation of black pigment solution: Add 0.01g of aniline black particles to a mortar and grind for 10min to make it into powder. Then add the aniline black powder to a centrifuge tube and add 0.5mL of deionized water. Mix well with a vortex mixer for 5min.

[0075] (2) Preparation of Nafion-aniline black solution: Add 5g Nafion solution and 0.1g DMAC solution to aniline black solution, then sonicate the mixture in an ice bath at 300W for 40min to obtain Nafion-aniline black solution, which is fully dispersed. Then, vacuum the Nafion-aniline black solution for 15min to remove internal gas impurities.

[0076] (3) Preparation of Nafion-aniline black film: Use a pipette to drop 2 mL of the treated Nafion-aniline black solution onto a 25×75 mm glass slide, and then heat it at 30 °C for 2 h in a vacuum drying oven. After drying, immerse the glass slide with Nafion-aniline black in deionized water for 10 s, and the film (thickness of 30 μm) can be automatically peeled off from the glass slide.

[0077] (4) Preparation of Nafion / aniline black / polyethylene optical drive film: stretch a single-sided adhesive polyethylene tape 10 mm along its length and then lay it flat (the tape thickness is 30 μm). Then attach the Nafion-aniline black film to the polyethylene to obtain the rolled optical drive film.

[0078] Example 4:

[0079] A method for preparing a photosensitive deformable optical drive film includes the following steps:

[0080] (1) Preparation of black pigment solution: Add 0.1g of aniline black particles to a mortar and grind for 10min to make it into powder. Then add the aniline black powder to a centrifuge tube and add 2mL of deionized water. Mix well with a vortex mixer for 15min.

[0081] (2) Preparation of Nafion-aniline black solution: Add 1g Nafion solution and 0.1g DMAC solution to aniline black solution, then sonicate the mixture in an ice bath at 300W for 20min to obtain Nafion-aniline black solution, which is fully dispersed. Then, vacuum the Nafion-aniline black solution for 5min to remove internal gas impurities.

[0082] (3) Preparation of Nafion-aniline black film: Use a pipette to drop 2 mL of the treated Nafion-aniline black solution onto a 25×75 mm glass slide, and then heat it at 80 °C for 2 h in a vacuum drying oven. After drying, immerse the glass slide with Nafion-aniline black in deionized water for 10 s, and the film (thickness of 30 μm) can be automatically peeled off from the glass slide.

[0083] (4) Preparation of Nafion / aniline black / polyethylene optical drive film: stretch the single-sided adhesive polyethylene 10 mm along the length direction and then unfold it flat (the thickness of the tape is 30 μm). Then attach the Nafion-aniline black film to the polyethylene to obtain the rolled optical drive film.

[0084] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a photosensitive deformable optical drive film, characterized in that, Includes the following steps: (1) Preparation of black pigment solution: Grind the black pigment particles into powder, then add deionized water and mix thoroughly; (2) Preparation of Nafion-black pigment solution: Nafion and DMAC are added to the black pigment solution in step (1), and the mixture is then ultrasonically treated to obtain Nafion-black pigment solution. The Nafion-black pigment solution is then vacuum-treated to remove internal gas impurities. (3) Preparation of Nafion-black pigment film: The Nafion-black pigment solution prepared in step (2) is dropped onto a glass slide, then heated and dried, and the Nafion-black pigment film is peeled off the glass slide; (4) Preparation of Nafion / black pigment / polyethylene optical drive film: Unfold and lay the single-sided adhesive polyethylene tape flat, and then attach the Nafion-black pigment film to the polyethylene tape to obtain the optical drive film.

2. The method for preparing a photosensitive deformable optical drive film according to claim 1, characterized in that, In step (1), the ratio of the mass of black pigment to the volume of deionized water is (0.01-0.1) g : (0.5-2) mL.

3. The method for preparing a photosensitive deformable optical drive film according to claim 1, characterized in that, The black pigment is made of one or more of aniline black, insulating carbon black, and copper chromium black.

4. The method for preparing a photosensitive deformable optical drive film according to claim 1, characterized in that, In step (2), the mass ratio of Nafion to DMAC is (1-5):(0.1-1).

5. The method for preparing a photosensitive, deformable optical drive film according to claim 1, characterized in that, In step (2), the ultrasonic power is 300W and the ultrasonic time is 20-40min.

6. The method for preparing a photosensitive, deformable optical drive film according to claim 1, characterized in that, The vacuum extraction time in step (2) is 5-15 minutes.

7. The method for preparing a photosensitive deformable optical drive film according to claim 1, characterized in that, The heating temperature in step (3) is 30-80℃, and the heating time is 2-6h.

8. The method for preparing a photosensitive deformable optical drive film according to claim 1, characterized in that, The heating temperature in step (3) is 50°C, and the heating time is 4 hours.

9. A photodiode film prepared by any one of claims 1-8.

10. The application of the photoelectric drive film according to claim 9 in biomimetic actuators and photoelectric conversion triboelectric nanogenerators.

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