Preparation method of legume biomass-derived carbon-based composite flexible electrode film with flower-like micro-nano structure and application thereof

Abstract

The application discloses a preparation method of a legume biomass-derived carbon-based composite flexible electrode film with flower-shaped micro-nano structures and application thereof, and belongs to the technical field of biomass-derived carbon materials and triboelectric nanogenerators. The preparation method comprises the following steps: after legume biomass raw materials are cleaned, dried, crushed and sieved, the legume biomass raw materials are mixed with an activating agent and pyrolysis activation is performed under a protective atmosphere to obtain legume biomass-derived porous carbon materials; the porous carbon materials are used as a matrix, and hydrothermal modification is performed in a reaction solution containing a metal precursor, so that metal components grow in situ on the surface of the carbon matrix to form flower-shaped micro-nano structures without a template to obtain a composite material; and the composite material is mixed with a high polymer film-forming material solution and an acidic component, dried to form a film, and a composite flexible electrode film is obtained. The application realizes high-value utilization of legume biomass resources, and the obtained composite carbon material has both a porous carbon skeleton and flower-shaped micro-nano structures.

Description

Technical Field

[0001] This invention relates to the fields of biomass-derived carbon materials, flexible functional membranes, and triboelectric nanogenerators, specifically to a method for preparing a bean biomass-derived carbon-based composite flexible electrode membrane with a flower-like micro / nano structure and its application. Background Technology

[0002] With the rapid development of flexible electronic devices, wearable devices, and self-powered sensing systems, triboelectric nanogenerators, which can effectively convert low-frequency mechanical energy in the environment into electrical energy, have attracted widespread attention. Triboelectric nanogenerators are characterized by simple structure, wide availability of materials, and strong environmental adaptability, and have application potential in distributed energy harvesting, human motion monitoring, and driving portable electronic devices.

[0003] In existing technologies, to improve the output performance of triboelectric nanogenerators, many studies and patents focus on controlling the surface structure of the triboelectric layer. For example, methods such as template replication, surface roughening, etching, or surface patterning are used to construct micro / nano structures on the surface of the triboelectric layer to increase the effective contact area and improve surface charge density. For instance, patent CN103780120A uses a template with surface roughening to prepare a polymer film with micro / nano-scale irregularities on its surface and applies it to a flexible triboelectric nanogenerator. While these methods can improve the contact efficiency of the triboelectric layer to some extent, their technical approach mainly revolves around the surface structure of the triboelectric layer and typically relies on template construction, surface replication, or additional patterning steps, making the process relatively complex.

[0004] Furthermore, most existing methods for introducing micro / nano structures through template methods, etching methods, or replication methods construct these structures on the surface of the friction layer, rather than directly forming active micro / nano structures in situ on the conductive electrode substrate. These methods not only increase the number of fabrication steps and process complexity, but also leave room for further optimization in terms of material interface bonding, flexible packaging adaptation, and long-term device stability. In particular, existing disclosures regarding technologies that use biomass-derived carbon materials as a conductive framework and grow flower-like micro / nano structures in situ on their surface without templates to enhance electrode layer functionality are still relatively limited.

[0005] Therefore, it is still necessary to develop a new technical solution: using porous carbon materials derived from legume biomass as a matrix, flower-like micro-nano structures are grown in situ on the carbon matrix surface without templates, and then combined with a polymer film-forming system to form a flexible electrode film, which is further encapsulated and assembled into a triboelectric nanogenerator device, thereby taking into account multiple needs such as biomass resource utilization, enhanced electrode layer function, flexible film formation and stable device output. Summary of the Invention

[0006] The purpose of this invention is to address the problems in existing technologies where the performance improvement schemes for triboelectric nanogenerators (TENGs) mostly focus on the surface structure control of the triboelectric layer, with relatively insufficient consideration of the role of the electrode layer in charge collection, storage and transport processes, as well as the problems that some micro-nano structure construction methods rely on templates and have relatively cumbersome processes. The invention proposes a method for preparing a flexible carbon-based composite electrode film derived from legume biomass with a flower-like micro-nano structure.

[0007] To solve the above-mentioned technical problems, the invention provides the following technical solution: a method for preparing a flexible carbon-based composite electrode film derived from legume biomass with a flower-like micro / nano structure, comprising the following steps:

[0008] S1. Pyrolysis activation: After washing, drying, crushing and sieving the legume biomass raw material, it is mixed with the activator in a certain proportion and pyrolyzed and activated under a protective atmosphere. After cooling, acid washing, water washing and drying, the legume biomass-derived porous carbon material is obtained.

[0009] S2. Hydrothermal modification: Using the soybean biomass-derived porous carbon material prepared in step S1 as the matrix, it is added to a reaction solution containing a metal precursor. After stirring and dispersing, a hydrothermal reaction is carried out. Then, after washing and drying, a soybean biomass-derived carbon composite material loaded with metal components is obtained.

[0010] S3. Electrode fabrication: The metal component-loaded bean biomass-derived carbon composite material obtained in step S2 is mixed with a polymer film-forming material solution and acidic components in a certain proportion, heated and stirred to form a uniform composite slurry, and then dried to form a film to obtain a flexible electrode film.

[0011] S4. Fabrication of triboelectric nanogenerator: The flexible electrode film prepared in step S3 is used as the intermediate electrode layer, and a mixture of organosilicon polymer material and polar solvent is used as the triboelectric layer to encapsulate it, thereby constructing a sandwich-type triboelectric nanogenerator device.

[0012] As a further aspect of the present invention, in step S1, the legume biomass raw material is one or more of legume outer skin, legume pod shells, and legume processing by-products; the legume outer skin includes one or more of broad bean pods, pea pods, soybean pods, mung bean pods, red bean pods, black bean pods, kidney bean pods, chickpea pods, and lentil pods; the legume pod shells include one or more of broad bean pod shells, pea pod shells, green bean pod shells, cowpea pod shells, lentil pod shells, and common bean pod shells; the legume processing by-products include one or more of legume peeling by-products, legume screening residues, legume cleaning debris, legume sorting waste, legume product processing residues, soybean meal, and soybean residue.

[0013] As a further embodiment of the present invention, in step S1, the activator is one or more of KOH, NaOH, K2CO3, Na2CO3, KHCO3, NaHCO3, and ZnCl2; the mass ratio of the legume biomass raw material to the activator is 5:1 to 20:1; the protective atmosphere is CO2, N2, or an inert mixed atmosphere; the pyrolysis activation temperature is 500 to 900°C; and the pyrolysis activation time is 10 to 120 minutes.

[0014] As a further aspect of the present invention, the metal precursor in step S2 includes a nickel salt and a manganese salt, wherein the nickel salt is one of nickel chloride, nickel nitrate, and nickel sulfate, and the manganese salt is one of manganese chloride, manganese nitrate, and manganese sulfate; the molar ratio of the nickel salt to the manganese salt is 1:1 to 5:1; the reaction solution also contains a precipitant, wherein the precipitant is one or more of urea, hexamethylenetetramine, and ammonia; the hydrothermal reaction temperature is 100 to 180°C, and the reaction time is 6 to 24 hours; under the hydrothermal reaction conditions, the nickel-manganese bimetallic component is in situ loaded on the surface of the soybean biomass-derived porous carbon material and forms a flower-like micro / nano structure.

[0015] As a further aspect of the present invention, the surface of the soybean biomass-derived carbon composite material loaded with metal components obtained in step S2 has a flower-like micro-nano structure. The flower-like micro-nano structure is a three-dimensional flower-like structure formed by cross-linking, stacking, or radial assembly of sheet-like, needle-like, or granular basic units.

[0016] As a further embodiment of the present invention, the polymeric film-forming material in step S3 is one or more of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl methylcellulose, and hydroxypropyl cellulose; the acidic component is one or more of phosphoric acid, hydrochloric acid, sulfuric acid, citric acid, and tartaric acid.

[0017] As a further embodiment of the present invention, in step S3, the mass fraction of the polymer film-forming material solution is 5-15 wt%; the mass percentage of the metal component-loaded bean biomass-derived carbon composite material in the composite slurry is 5-30 wt%; the mass percentage of the acidic component in the composite slurry is 5-25 wt%; the composite slurry is dried in an oven for 2-5 hours at a temperature of 45-75°C, and the dried material is the flexible electrode film.

[0018] As a further embodiment of the present invention, the organosilicon polymer material in step S4 is polydimethylsiloxane; the polar solvent is deionized water, which is used to adjust the flexibility of the encapsulation layer and promote the formation of a porous structure; the flexible electrode film is located between the upper and lower encapsulation layers to form a sandwich structure triboelectric nanogenerator device.

[0019] As a further embodiment of the present invention, the polydimethylsiloxane is formed by mixing a prepolymer and a curing agent, wherein the mass ratio of the prepolymer to the curing agent is 10:1; the volume ratio of the organosilicon polymer to the polar solvent is (4-8):1; the thickness of the electrode material is 0.5-6 mm; the thickness of the friction layer is 0.1-3 cm; and the area of ​​the electrode material is smaller than the area of ​​the upper and lower encapsulation layers.

[0020] Compared with the prior art, this invention has the following beneficial effects:

[0021] 1. This invention uses legume biomass as raw material and converts it into carbon material with a porous structure through pyrolysis activation. Not only is the raw material source wide and the cost low, but it also facilitates the resource utilization of agricultural or food processing by-products and reduces the dependence on traditional metal electrode materials or commercial conductive fillers.

[0022] 2. This invention first constructs a porous carbon framework derived from legume biomass through pyrolysis activation, and then grows flower-like micro / nano structures in situ on the carbon matrix surface through hydrothermal modification, achieving interface structure control without the need for additional templates. The resulting composite material simultaneously possesses a high specific surface area, abundant interfacial active sites, and a relatively reasonable pore structure, which is beneficial for enhancing the charge-carrying capacity of the electrode layer.

[0023] 3. Unlike existing technologies that mainly focus on the micro-nano structure control of the tribological layer surface, this invention starts from the electrode layer. Through the synergistic effect of flower-like micro-nano structures and porous carbon skeletons, it can increase interface roughness, improve effective contact and polarization capabilities, and improve charge collection, storage and transport processes, thereby helping to improve the overall output performance of triboelectric nanogenerators.

[0024] 4. The TENG of this invention can achieve an output voltage of not less than 350V, an output current of not less than 5μA, and an output current of not less than 900mW / m. 2 The high power density not only solves the problem of waste bean biomass disposal, but also expands the application of biochar in the field of energy harvesting, which has the dual significance of energy utilization and environmental protection. Attached Figure Description

[0025] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are merely some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without any creative effort.

[0026] Figure 1 This is a flowchart of the method of the present invention;

[0027] Figure 2This is a SEM image of the bean biomass-derived carbon composite material with a flower-like micro / nano structure from Example 1;

[0028] Figure 3 This is a test diagram of the open-circuit voltage and short-circuit current of the TENG in Example 1;

[0029] Figure 4 This is a power density test graph of TENG in Example 1;

[0030] Figure 5 This is a schematic diagram of Example 1, showing how a commercial capacitor is charged to power a calculator;

[0031] Figure 6 This is a schematic diagram showing the different voltage waveforms and magnitudes generated by impacts and knocks on different parts of the hand in Embodiment 1. Detailed Implementation

[0032] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and 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.

[0033] Example 1:

[0034] See Figure 1 The flexible electrode made of biomass-derived carbon material was applied to TENG and tested. The specific steps are as follows:

[0035] Step 1: Broad bean husks were used as the raw material for legume biomass. The surface of the broad bean husks was first thoroughly washed with deionized water to remove dust and surface impurities. Then, they were placed in an oven and dried at 105℃ for 24 hours. After drying, the broad bean husks were removed, pulverized, and sieved through a 60-mesh sieve. The sieved powder was used for subsequent experiments. The broad bean husk powder was weighed and mixed uniformly with KOH at a mass ratio of 9:1. The mixture was then placed in a tube furnace under a CO2 atmosphere and pyrolyzed at 700℃ for 30 minutes. After the product cooled naturally to room temperature, it was repeatedly washed with 1 mol / L HCl solution and deionized water to remove residual activator and inorganic impurities. It was then placed in an oven and dried at 105℃ for 24 hours to obtain the broad bean husk-derived porous carbon material, denoted as BBC.

[0036] Step 2: Dissolve 4.5 mmol of NiCl2·6H2O, 1.5 mmol of MnCl2·4H2O, and 12 mmol of urea in 60 mL of deionized water, stirring until fully dissolved to obtain a homogeneous reaction solution. Add 0.8 g of BBC to the above reaction solution, continue stirring to disperse it evenly, and then transfer the resulting mixture to a polytetrafluoroethylene-lined high-pressure reactor. React at 120 °C for 12 h. After the reaction is complete and naturally cooled to room temperature, remove the product, wash it repeatedly with ethanol and deionized water, and then place it in an oven to dry thoroughly at 70 °C to obtain a legume biomass-derived carbon composite material with a flower-like micro / nano structure, denoted as BBC@NiMn. Morphological characterization shows that the nickel-manganese bimetallic component can grow in situ on the BBC surface without a template to form a flower-like micro / nano structure, thereby improving the surface roughness and the number of interfacial active sites.

[0037] Step 3: PVA-1799 powder was slowly added to deionized water and stirred continuously in a 90°C water bath until a uniform and transparent 10wt% polyvinyl alcohol solution was obtained. Then, BBC@NiMn prepared in Step 2 and phosphoric acid were added to the polyvinyl alcohol solution, wherein the mass percentage of phosphoric acid in the composite slurry was 15wt% (the phosphoric acid content in the phosphoric acid solution used was 85wt%), and the mass percentage of BBC@NiMn in the composite slurry was 12wt%. The mixture was mechanically stirred for 3 hours to obtain a uniformly dispersed composite slurry. The composite slurry was then dried in an oven to form a film, which is a bean biomass-derived carbon-based composite flexible electrode film with a flower-like micro / nano structure.

[0038] Step 4: Polydimethylsiloxane (PDMS) prepolymer and curing agent were uniformly mixed at a mass ratio of 10:1, and then mixed with deionized water at a volume ratio of 5:1 and stirred uniformly for 30 minutes to obtain a PDMS mixture system for encapsulation. First, this mixture system was poured into a petri dish and cured in a 70°C oven to form a bottom PDMS layer, serving as the bottom friction layer of the device. Then, the composite flexible electrode film prepared in Step 3 was placed on the bottom PDMS layer and further dried and fixed at 50°C to form an intermediate electrode layer. Next, the above PDMS mixture system was placed over the intermediate electrode layer and cured in an oven to form a top PDMS layer. Copper foil was used as a lead-out wire to finally obtain a sandwich-type triboelectric nanogenerator device, denoted as BBC@NiMn-TENG. The fabricated device is flexible, bendable, and foldable, making it easy to carry and integrate.

[0039] Step 5: The prepared BBC@NiMn-TENG was mounted on the testing device, and its output performance was tested. The test results show that the device has stable output performance, with an open-circuit voltage of up to 440V, a short-circuit current of up to 7.79μA, and a power density of up to 1341mW / m². 2 Furthermore, the fabricated device, when used to drive small electronic devices such as calculators, can achieve stable power supply, indicating its promising application potential in mechanical energy harvesting. In addition, the device can output different electrical signal responses to different mechanical stimuli, making it suitable for self-powered sensing fields such as human motion monitoring.

[0040] Example 2:

[0041] The same method as in Example 1 was used to prepare the soybean biomass-derived porous carbon material BBC. The difference was that the hydrothermal modification process in step 2 was not performed when preparing the composite flexible electrode membrane. That is, the BBC electrode was used instead of the BBC@NiMn electrode. The remaining steps were the same as in Example 1.

[0042] The BBC-TENG obtained in this embodiment, under the same test conditions, exhibited an open-circuit voltage of 320V, a short-circuit current of 5.12μA, and a short-circuit current of 897mW / m. 2 The power density is high; in practical applications, this TENG can also realize energy harvesting and self-powered sensing applications.

[0043] The biggest difference between Example 2 and Example 1 is that no flower-like micro / nanostructures were grown in situ on the surface of the porous carbon matrix derived from legume biomass. Therefore, although the resulting device can still achieve mechanical energy harvesting and self-powered sensing applications, its output performance is lower than that of Example 1, indicating that constructing flower-like micro / nanostructures on the carbon matrix surface helps to improve the overall performance of the electrode layer in charge harvesting, storage, and transport processes.

[0044] Example 3:

[0045] Step 1: Use cowpea pods as waste biomass; other steps are the same as in Example 1.

[0046] Furthermore, the TENG obtained in this embodiment, under the same test conditions, exhibited an open-circuit voltage of 402V, a short-circuit current of 7.06μA, and a short-circuit current of 1275mW / m. 2 The power density is high; in practical applications, this TENG can also realize energy harvesting and self-powered sensing applications.

[0047] This example demonstrates that the electrical output performance of TENG decreases slightly depending on the type of legume biomass used.

[0048] Example 4:

[0049] Cowpea pods were used as waste biomass; 14 wt% biomass carbon material was added when making the electrode material; other aspects were the same as in Example 1.

[0050] Furthermore, the TENG obtained in this embodiment, under the same test conditions, exhibited an open-circuit voltage of 369V, a short-circuit current of 6.44μA, and a short-circuit current of 988mW / m. 2 The power density is high; in practical applications, this TENG can also realize energy harvesting and self-powered sensing applications.

[0051] This embodiment shows that when the amount of biomass carbon material added during the preparation of electrode materials increases, it may cause changes in the conductive network and mechanical state inside the electrode film, thereby significantly reducing the electrical output performance of TENG and the device sensitivity.

[0052] Example 5:

[0053] Soybean residue was used as waste biomass, and the amounts of NiCl2·6H2O and MnCl2·4H2O added were 6 mmol and 1.5 mmol, respectively; other aspects were the same as in Example 1.

[0054] Furthermore, the TENG obtained in this embodiment, under the same test conditions, exhibited an open-circuit voltage of 368V, a short-circuit current of 5.94μA, and a short-circuit current of 928mW / m. 2 The power density is high; in practical applications, it can also realize energy harvesting and self-powered sensing applications.

[0055] This embodiment shows that when the molar ratio of nickel salt to manganese salt increases, the electrical output performance of the resulting TENG decreases, indicating that the metal precursor ratio has a significant impact on the formation state of the flower-like micro / nano structure on the surface of the composite material and its electrical output behavior.

[0056] Example 6:

[0057] Soybean residue was used as waste biomass, and 20 wt% phosphoric acid was added when making electrode materials; otherwise, it was the same as in Example 1.

[0058] Furthermore, the TENG obtained in this embodiment, under the same test conditions, exhibited an open-circuit voltage of 468V, a short-circuit current of 8.06μA, and a short-circuit current of 1392mW / m. 2 The power density is high; in practical applications, it can also realize energy harvesting and self-powered sensing applications.

[0059] This embodiment demonstrates that appropriately increasing the amount of phosphoric acid added during the preparation of electrode materials helps to improve the interfacial state of the composite electrode film, thereby improving the electrical output performance of TENG.

[0060] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A method for preparing a flexible carbon-based composite electrode film derived from legume biomass with a flower-like micro / nano structure, characterized in that: The steps include the following: S1. Pyrolysis activation: After washing, drying, crushing and sieving the legume biomass raw material, it is mixed with the activator in a certain proportion and pyrolyzed and activated under a protective atmosphere. After cooling, acid washing, water washing and drying, the legume biomass-derived porous carbon material is obtained. S2. Hydrothermal modification: Using the soybean biomass-derived porous carbon material prepared in step S1 as the matrix, it is added to a reaction solution containing a metal precursor. After stirring and dispersing, a hydrothermal reaction is carried out. Then, after washing and drying, a soybean biomass-derived carbon composite material loaded with metal components is obtained. S3. Electrode fabrication: The metal component-loaded bean biomass-derived carbon composite material obtained in step S2 is mixed with a polymer film-forming material solution and acidic components in a certain proportion, heated and stirred to form a uniform composite slurry, and then dried to form a film to obtain a flexible electrode film. S4. Fabrication of triboelectric nanogenerator: The flexible electrode film prepared in step S3 is used as the intermediate electrode layer, and a mixture of organosilicon polymer material and polar solvent is used as the triboelectric layer to encapsulate it, thereby constructing a sandwich-type triboelectric nanogenerator device.

2. The method for preparing a flexible carbon-based composite electrode film derived from legume biomass with a flower-like micro / nano structure according to claim 1, characterized in that: In step S1, the legume biomass raw material is one or more of legume outer skin, legume pods, and legume processing by-products; the legume outer skin includes one or more of broad bean pods, pea pods, soybean pods, mung bean pods, red bean pods, black bean pods, kidney bean pods, chickpea pods, and lentil pods; the legume pods include one or more of broad bean pods, pea pods, green bean pods, cowpea pods, lentil pods, and common bean pods; the legume processing by-products include one or more of legume peeling by-products, legume screening residues, legume cleaning debris, legume sorting waste, legume product processing residues, soybean meal, and soybean residue.

3. The method for preparing a flexible carbon-based composite electrode film derived from legume biomass with a flower-like micro / nano structure according to claim 1, characterized in that: In step S1, the activator is one or more of KOH, NaOH, K2CO3, Na2CO3, KHCO3, NaHCO3, and ZnCl2; the mass ratio of the legume biomass raw material to the activator is 5:1 to 20:1; the protective atmosphere is CO2, N2, or an inert mixed atmosphere; the pyrolysis activation temperature is 500 to 900℃; and the pyrolysis activation time is 10 to 120 min.

4. The method for preparing a flexible carbon-based composite electrode film derived from legume biomass with a flower-like micro / nano structure according to claim 1, characterized in that: The metal precursor in step S2 includes a nickel salt and a manganese salt. The nickel salt is one of nickel chloride, nickel nitrate, and nickel sulfate, and the manganese salt is one of manganese chloride, manganese nitrate, and manganese sulfate. The molar ratio of the nickel salt to the manganese salt is 1:1 to 5:

1. The reaction solution also contains a precipitant, which is one or more of urea, hexamethylenetetramine, and ammonia. The hydrothermal reaction temperature is 100 to 180°C, and the reaction time is 6 to 24 hours. Under the hydrothermal reaction conditions, the nickel-manganese bimetallic component is in situ loaded on the surface of the soybean biomass-derived porous carbon material and forms a flower-like micro / nano structure.

5. The method for preparing a flexible carbon-based composite electrode film derived from legume biomass with a flower-like micro / nano structure according to claim 1, characterized in that: The surface of the bean biomass-derived carbon composite material loaded with metal components obtained in step S2 has a flower-like micro-nano structure. The flower-like micro-nano structure is a three-dimensional flower-like structure formed by cross-linking, stacking or radial assembly of sheet-like, needle-like or particulate basic units.

6. The method for preparing a flexible carbon-based composite electrode film derived from legume biomass with a flower-like micro / nano structure according to claim 1, characterized in that: The polymeric film-forming material mentioned in step S3 is one or more of polyvinyl alcohol, polyvinylpyrrolidone, hydroxypropyl methylcellulose, and hydroxypropyl cellulose; the acidic component is one or more of phosphoric acid, hydrochloric acid, sulfuric acid, citric acid, and tartaric acid.

7. The method for preparing a flexible carbon-based composite electrode film derived from legume biomass with a flower-like micro / nano structure according to claim 6, characterized in that: In step S3, the mass fraction of the polymer film-forming material solution is 5-15 wt%; the mass percentage of the metal component-loaded bean biomass-derived carbon composite material in the composite slurry is 5-30 wt%; the mass percentage of the acidic component in the composite slurry is 5-25 wt%; the composite slurry is dried in an oven for 2-5 hours at a temperature of 45-75°C, and the dried material is the flexible electrode film.

8. The method for preparing a flexible carbon-based composite electrode film derived from legume biomass with a flower-like micro / nano structure according to claim 1, characterized in that: The organosilicon polymer material mentioned in step S4 is polydimethylsiloxane; the polar solvent is deionized water, which is used to adjust the flexibility of the encapsulation layer and promote the formation of a porous structure; the flexible electrode film is located between the upper and lower encapsulation layers to form a sandwich structure triboelectric nanogenerator device.

9. The method for preparing a flexible carbon-based composite electrode film derived from legume biomass with a flower-like micro / nano structure according to claim 8, characterized in that: The polydimethylsiloxane is formed by mixing a prepolymer and a curing agent, with a mass ratio of prepolymer to curing agent of 10:1; the volume ratio of the organosilicon polymer to the polar solvent is (4-8):1; the electrode material has a thickness of 0.5-6 mm; the friction layer has a thickness of 0.1-3 cm; and the area of ​​the electrode material is smaller than the area of ​​the upper and lower encapsulation layers.

10. The triboelectric nanogenerator device prepared by the method of preparing a bean biomass-derived carbon-based composite flexible electrode film with a flower-like micro-nano structure as described in any one of claims 1-9 can be used in mechanical energy harvesting, self-powered sensing, human motion monitoring, or flexible electronic devices.

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