WO2022062133A1 - Fully-degradable friction nano-generator, preparation method therefor and use thereof - Google Patents

Abstract

A fully-degradable friction nano-generator, a preparation method therefor and the use thereof. The fully-degradable friction nano-generator comprises a first friction layer and a second friction layer, wherein the first friction layer comprises a first amino acid composite material layer (11) and a first metal current collector layer (12) which are sequentially stacked; and the second friction layer comprises a second amino acid composite material layer (11) and a second metal current collector layer (12) which are sequentially stacked. By adding amino acids from a wide range of sources into the materials of the friction layers to form composite materials, amino acid crystal compounds with different functional groups are introduced to the surfaces of the materials of the friction layers, such that the electron gain and loss capacities of the friction layers are greatly differentiated, the purpose of effectively improving the electricity output performance of the friction nano-generator is achieved, and the electrical output performance is adjustable.

Description

A fully degradable triboelectric nanogenerator and its preparation method and application technical field

The invention belongs to the technical field of medical devices, and relates to a triboelectric nanogenerator, a preparation method and application thereof, in particular to a fully degradable triboelectric nanogenerator, a preparation method and application thereof, and in particular to a fully degradable triboelectric generator with high electrical output performance. Degradable triboelectric nanogenerator and preparation method and application thereof.

Background technique

Implantable Medical Devices (IMDs for short) have been widely used in clinical medicine due to their advantages of dexterity and convenience, real-time monitoring of patients' health status, and effective treatment of various emergencies. At present, the key factor restricting the development of active IMDs is energy supply. The power of most active IMDs is mainly provided by the built-in battery. Once the battery power is exhausted, the IMDs will stop working normally.

Triboelectric nanogenerators (TENGs) are a new type of energy harvesting technology developed in recent years, which have been proven to efficiently harvest the mechanical energy generated by the movement of tissues or organs in vivo and convert it into electrical output. The electrical energy output converted by TENG can be used to charge the batteries of IMDs, which provides a new option for the power source of IMDs.

At present, due to the replacement and damage of electronic products, a large amount of electronic waste (E-waste) is continuously generated around the world every year. These discarded e-wastes usually contain a large amount of toxic and harmful metal or non-metal elements. Traditional landfill and incineration methods have catastrophic consequences for human living environments such as water, land and air. Therefore, the development of low-toxicity, environmentally friendly, renewable, and degradable new materials to replace some components of current electronic products or to prepare new electronic devices with completely zero waste emissions is the mainstream development direction in the future. Transient electrons are an emerging electronic device fabrication technology developed in recent years. It means that after the device completes the specified function, its physical form and function can be partially or completely disappeared immediately under the trigger of external stimuli. The emergence of transient electronic technology can greatly improve the serious E-waste pollution problem that occurs after electronic products are scrapped in the traditional sense.

Applying transient electronic technology to the field of IMDs, the device can degrade in the living body and be metabolized or absorbed by the human body after the device completes its function, and the patient can avoid the process of removing the device by a second operation, which will greatly reduce the pain of the patient. , reduce the potential surgical risk and inflammatory response, reduce medical costs and prevent the waste of medical resources.

The electrical output performance of triboelectric nanogenerators largely depends on the amount of charge transfer between the friction layer materials, and the amount of charge transfer is closely related to the molecular components constituting the surface material of the friction layer, and molecules with different functional groups show different electronic gain and loss capability. Due to the single composition of the friction layer material selected by the current fully degradable triboelectric nanogenerator, the electron gain and loss ability between the friction layers is similar or the same, which in turn reduces the amount of transferred charges and the electrical output performance of the triboelectric nanogenerator.

SUMMARY OF THE INVENTION

In view of the deficiencies of the prior art, the purpose of the present invention is to provide a triboelectric nanogenerator and its preparation method and application, specifically a fully degradable triboelectric nanogenerator and its preparation method and application, especially to provide an electrical output A fully degradable triboelectric nanogenerator with high performance and its preparation method and application.

In order to achieve this object of the invention, the present invention adopts the following technical solutions:

In a first aspect, the present invention provides a fully degradable triboelectric nanogenerator. The fully degradable triboelectric nanogenerator includes a first friction layer and a second friction layer; the first friction layer includes a first friction layer that is stacked in sequence. An amino acid composite material layer and a first metal current collector layer; the second friction layer includes a second amino acid composite material layer and a second metal current collector layer stacked in sequence.

In the invention, amino acid crystal compounds with different functional group structures are introduced on the surface of the friction layer material by adding amino acids to the friction layer material to form a composite material, thereby greatly differentiating the electronic gain and loss ability between the friction layers and effectively improving the friction The purpose of nanogenerator electrical output performance. At the same time, the present invention is also the first to propose to use amino acid material as the friction layer electrode material of the fully degradable triboelectric nanogenerator, which is a new type of implantable fully degradable triboelectric nanogenerator structure.

Preferably, the preparation raw materials of the first amino acid composite material layer include amino acids and/or amino acid derivatives, and also include polymer materials.

The raw materials for the preparation of the first amino acid composite material layer in the nanogenerator of the present invention include amino acids and/or amino acid derivatives, and polymer materials.

The polymer materials include collagen, gelatin, soybean protein, egg white, silk fibroin, sodium alginate, cellulose, lignin, chitin, chitosan, hyaluronic acid, polyethylene oxide, polycaprolactone, poly Any one or a combination of at least two of lactic acid, polylactic acid-glycolic acid copolymer, polyvinyl alcohol, microbial polyester, polydioxanone, or polyanhydride.

The polymer materials involved in the present invention are all polymer materials with good biocompatibility and bioabsorbability, so that the prepared nanogenerators not only have fully degradable properties, but also can be implanted in vivo.

The combination of the at least two types, such as the combination of egg white and silk fibroin, the combination of sodium alginate and cellulose, the combination of chitosan and hyaluronic acid, etc., can be selected from any other combination, which will not be omitted here. Repeat them one by one.

Preferably, the mass ratio of the amino acid and/or amino acid derivative to the polymer material is (0.1-2.0):1, such as 0.1:1, 0.2:1, 0.4:1, 0.5:1, 0.8:1, 1.0 :1, 1.2:1, 1.4:1, 1.6:1, 1.8:1 or 2.0:1, etc. Any specific point value within the above range can be selected, and will not be repeated here.

The specific selection of the mass ratio of the amino acid and/or amino acid derivative to the polymer material is (0.1-2.0): 1 because if the ratio of the polymer material is further increased, the relative amount of the amino acid and/or amino acid derivative added It is very rare, resulting in low electrical output performance of triboelectric nanogenerators; if the proportion of polymer materials is further reduced, composite membrane electrode materials cannot be effectively prepared.

Preferably, the preparation raw materials of the second amino acid composite material layer include amino acids and/or amino acid derivatives, and also include polymer materials.

The raw materials for the preparation of the second amino acid composite material layer in the nanogenerator of the present invention include amino acids and/or amino acid derivatives, and polymer materials.

The polymer materials include collagen, gelatin, soybean protein, egg white, silk fibroin, sodium alginate, cellulose, lignin, chitin, chitosan, hyaluronic acid, polyethylene oxide, polycaprolactone, poly Any one or a combination of at least two of lactic acid, polylactic acid-glycolic acid copolymer, polyvinyl alcohol, microbial polyester, polydioxanone, or polyanhydride.

The polymer materials involved in the present invention are all polymer materials with good biocompatibility and bioabsorbability, so that the prepared nanogenerators not only have fully degradable properties, but also can be implanted in vivo.

The combination of the at least two types, such as the combination of egg white and silk fibroin, the combination of sodium alginate and cellulose, the combination of chitosan and hyaluronic acid, etc., can be selected from any other combination, which will not be omitted here. Repeat them one by one.

Preferably, the mass ratio of the amino acid and/or amino acid derivative to the polymer material is (0.1-2.0):1, such as 0.1:1, 0.2:1, 0.4:1, 0.5:1, 0.8:1, 1.0 :1, 1.2:1, 1.4:1, 1.6:1, 1.8:1 or 2.0:1, etc. Any specific point value within the above range can be selected, and will not be repeated here.

The specific selection of the mass ratio of the amino acid and/or amino acid derivative to the polymer material is (0.1-2.0): 1 because if the ratio of the polymer material is further increased, the relative amount of the amino acid and/or amino acid derivative added It is very rare, resulting in low electrical output performance of triboelectric nanogenerators; if the proportion of polymer materials is further reduced, composite membrane electrode materials cannot be effectively prepared.

Preferably, the preparation raw materials of the first metal current collector layer and the second metal current collector layer are independently selected from any one or a combination of at least two of magnesium, molybdenum, tungsten or iron.

The combination of the at least two types, such as the combination of magnesium and molybdenum, the combination of molybdenum and tungsten, the combination of tungsten and iron, etc., can be selected from any other combination, which will not be repeated here.

Preferably, the first friction layer further includes a first base layer overlapping the first amino acid composite material layer and the first metal current collector layer.

Preferably, the second friction layer further includes a second base layer overlapping the second amino acid composite material layer and the second metal current collector layer.

According to the mechanical properties of the first amino acid composite material layer and the second amino acid composite material layer, they can be directly used for the preparation of the friction layer, or can be adhered to the base layer and then used for the preparation of the friction layer.

Preferably, the thickness of the first base layer is 10-5000 μm, such as 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm, 500 μm, 1000 μm, 2000 μm, 3000 μm, 4000 μm or 5000 μm, etc., within the above numerical ranges Other specific point values of , can be selected, and will not be repeated here.

Preferably, the thickness of the second base layer is 10-5000 μm, such as 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm, 500 μm, 1000 μm, 2000 μm, 3000 μm, 4000 μm or 5000 μm, etc., within the above numerical ranges Other specific point values of , can be selected, and will not be repeated here.

Preferably, the preparation materials of the first base layer and the second base layer are independently selected from collagen, gelatin, soybean protein, egg white, silk fibroin, sodium alginate, cellulose, lignin, chitin, chitosan , hyaluronic acid, polyethylene oxide, polycaprolactone, polylactic acid, polylactic acid-co-glycolic acid copolymer, polyvinyl alcohol, microbial polyester, polydioxanone or any one or at least one of polyanhydrides combination of the two.

The combination of the at least two types, such as the combination of egg white and silk fibroin, the combination of sodium alginate and cellulose, the combination of chitosan and hyaluronic acid, etc., can be selected from any other combination, which will not be omitted here. Repeat them one by one.

Preferably, the thicknesses of the first amino acid composite material layer and the second amino acid composite material layer are independently 1-5000 μm, such as 1 μm, 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 400 μm, 500 μm, 1000 μm, 2000 μm, 3000 μm, 4000 μm or 5000 μm, etc., and other specific point values within the above numerical range can be selected, which will not be repeated here.

Preferably, the thicknesses of the first metal current collector layer and the second metal current collector layer are independently 10 nm-10 μm, such as 0.01 μm, 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 2 μm, 5 μm or 10 μm, etc. Other specific point values within the numerical range can be selected, which will not be repeated here.

In a second aspect, the present invention provides a preparation method of the above-mentioned fully degradable triboelectric nanogenerator, the preparation method comprising the steps of: the first amino acid composite material layer in the first friction layer and the second friction layer With the surface of the second amino acid composite material layer facing inward, and the first metal current collector layer and the second metal current collector layer facing outward, the fully degradable triboelectric nanogenerator of vertical contact separation type is assembled.

The distance between the first friction layer and the second friction layer is 0.1mm-100mm, for example, 0.1mm, 1mm, 5mm, 10mm, 20mm, 40mm, 50mm, 60mm, 80mm or 100mm, etc., other values within the above-mentioned range The specific point values can be selected, and will not be repeated here.

Preferably, after the fully degradable triboelectric nanogenerator is obtained, it can also be encapsulated. The encapsulation process is as follows: first, place the triboelectric nanogenerator in the middle position of a prepared encapsulation layer, and use another The same encapsulation layer is placed on the triboelectric nanogenerator and the upper and lower membranes are overlapped. According to the physical and chemical properties of the encapsulation layer material, the encapsulation layer and the base layer are connected to the base layer by hot-melt plastic sealing and smearing of material binders at the gaps around the upper and lower layers. It is tightly sealed to complete the package of the whole device.

Preferably, the preparation materials of the encapsulation layer include collagen, gelatin, soybean protein, egg white, silk fibroin, sodium alginate, cellulose, lignin, chitin, chitosan, hyaluronic acid, polycaprolactone, Any one or a combination of at least two of polylactic acid, polylactic acid-glycolic acid copolymer, polyvinyl alcohol, microbial polyester, polydioxanone or polyanhydride.

Preferably, the preparation method of the first friction layer comprises the following steps:

(1) mixing the preparation raw materials of the first amino acid composite material layer with a solvent, homogenizing, then casting film, spin coating, casting film or melting film, and drying to obtain the first amino acid composite material layer;

(2) preparing a first metal current collector layer by electroplating, spraying or magnetron sputtering on one side of the first amino acid composite material layer, and finally obtaining the first friction layer.

Preferably, the mass fraction of the homogenized polymer material is 1-20%, for example, 1%, 2%, 5%, 8%, 10%, 12%, 15% or 20%, etc., within the range of the above values Other specific point values of , can be selected, and will not be repeated here.

Preferably, the drying temperature is 40-80°C, such as 40°C, 50°C, 60°C, 70°C or 80°C, etc., and the drying time is 10-30h, such as 10h, 15h, 20h, 25h or 30h, etc., the above Other specific point values within the numerical range can be selected, which will not be repeated here.

Preferably, after the first amino acid composite material layer is obtained in step (1), it further includes step (1'): adhering the first base layer on one side of the first amino acid composite material layer; then on the first base layer away from the first base layer A first metal current collector layer is prepared on one side of the amino acid composite material layer by electroplating, spraying or magnetron sputtering, and finally the first friction layer is obtained.

Preferably, the preparation method of the first base layer comprises: mixing the preparation raw materials of the first base layer with a solvent, homogenizing, then casting into a film, spin coating, casting into a film or melting into a film, and drying to obtain first base layer.

Preferably, the preparation method of the second friction layer comprises the following steps:

(1) mixing the preparation raw materials of the second amino acid composite material layer with a solvent, homogenizing, then casting into a film, spin coating, casting into a film or melting into a film, and drying to obtain a second amino acid composite layer;

(2) preparing the second metal current collector layer by electroplating, spraying or magnetron sputtering on one side of the second amino acid composite material layer, and finally obtaining the second friction layer;

Preferably, the mass fraction of the homogenized polymer material is 1-20%, for example, 1%, 2%, 5%, 8%, 10%, 12%, 15% or 20%, etc., within the range of the above values Other specific point values of , can be selected, and will not be repeated here.

Preferably, the drying temperature is 40-80°C, such as 40°C, 50°C, 60°C, 70°C or 80°C, etc., and the drying time is 10-30h, such as 10h, 15h, 20h, 25h or 30h, etc., the above Other specific point values within the numerical range can be selected, which will not be repeated here.

Preferably, after the second amino acid composite material layer is obtained in step (1), it further includes step (1'): adhering the second base layer on one side of the second amino acid composite material layer; A second metal current collector layer is prepared on one side of the diamino acid composite material layer by electroplating, spraying or magnetron sputtering, and finally the second friction layer is obtained.

Preferably, the preparation method of the second base layer comprises: mixing the preparation raw materials of the second base layer with a solvent, homogenizing, then casting into a film, spin coating, casting into a film or melting into a film, and drying to obtain second base layer.

In a third aspect, the present invention provides an application of the above-mentioned fully degradable triboelectric nanogenerator in energy supply for implantable medical devices.

Compared with the prior art, the present invention has the following beneficial effects:

By adding amino acids from a wide range of sources into the friction layer material to form a composite material, the invention introduces amino acid crystal compounds with different functional group structures on the surface of the friction layer material, so as to greatly differentiate the electronic gain and loss ability between the friction layers, and achieve For the purpose of effectively improving the electrical output performance of the triboelectric nanogenerator, its open circuit voltage (V _OC ) can reach up to 45V, and its short-circuit current (I _SC ) can reach up to 0.48 μA, and the electrical output performance can be adjusted. The present invention proposes to use amino acid material as the electrode material of the friction layer of the fully degradable triboelectric nanogenerator for the first time, which is a new type of implantable fully degradable triboelectric nanogenerator structure.

Description of drawings

1 is a schematic structural diagram of the first amino acid composite material layer or the second amino acid composite material layer in Example 1;

2 is a schematic structural diagram of the first friction layer or the second friction layer in Example 1, wherein 11 is the first amino acid composite material layer or the second amino acid composite material layer; 12 is the first metal current collector layer or the second metal layer collector layer;

3 is a schematic structural diagram of the triboelectric nanogenerator in Example 1, wherein 11 is the first amino acid composite material layer or the second amino acid composite material layer; 12 is the first metal current collector layer or the second metal current collector layer.

detailed description

The technical solutions of the present invention are further described below through specific embodiments. It should be understood by those skilled in the art that the embodiments are only for helping the understanding of the present invention, and should not be regarded as a specific limitation of the present invention.

The sources of the polymer materials involved in the following examples are as follows:

Sodium alginate was purchased from Sigma-Aldrich as viscosity 15-25cP, 1% in _H2O .

Polyvinyl alcohol was purchased from Sigma-Aldrich under the model average M _w 130,000.

Silk fibroin was purchased from Suzhou Simeite Biotechnology Co., Ltd., and the model is molecular weight ≥ 100,000 Daltons.

Gelatin was purchased from Sigma-Aldrich, model number V900863.

Polyethylene oxide was purchased from Sigma-Aldrich, model average M _v 200000.

Example 1

The present embodiment provides a fully degradable triboelectric nanogenerator, and its preparation method is as follows:

(1) Preparation of the first amino acid composite material layer: firstly prepare an acetic acid solution with a volume fraction of 1%, then add the sodium alginate powder material into the acetic acid solution, and fully stir to obtain a homogeneous solution with a mass fraction of 3%. Next, add glycine powder to the sodium alginate solution to make the mass ratio of glycine and sodium alginine in the mixed solution to be 1.2:1, and stir well. Finally, the obtained mixed solution was poured into a clean glass dish, left standing at 25°C to remove air bubbles, and then placed in a vacuum drying oven at 60°C for 12 hours to obtain a flat first amino acid composite layer with a thickness of 300 μm. Its schematic diagram is shown in Figure 1.

(2) Preparation of the second amino acid composite material layer: firstly, the polyvinyl alcohol polymer material was added to the deionized aqueous solution, heated to 95° C. and fully stirred to obtain a polyvinyl alcohol aqueous solution with a mass fraction of 8%. Next, add serine powder to the polyvinyl alcohol solution to make the mass ratio of serine and polyvinyl alcohol in the mixed solution to be 0.45:1, and stir well. Finally, the obtained mixed solution was poured into a clean glass plate, left standing at 25°C to remove air bubbles, and then placed in a vacuum drying oven at 60°C for 18 hours to obtain a second amino acid composite layer with a thickness of 200 μm. Its schematic diagram is shown in Figure 1.

Since the composite material layer prepared above has good mechanical properties and can be used as a base layer at the same time, there is no need to prepare an additional base layer, and the composite material layer can be directly used in the friction layer structure.

(3) prepare the metal magnesium current collector layer by measuring and controlling sputtering on one side of the first amino acid composite material layer and the second amino acid composite material layer respectively, and the specific process is as follows: the composite material layer is placed on a magnetron sputtering apparatus In the cavity, sputtering parameters DC sputtering power 100W, duration 20min, a first metal current collector layer and a second metal current collector layer with a thickness of 500nm are obtained, and a first friction layer and a second friction layer are obtained simultaneously. Its schematic diagram is shown in Figure 2.

(4) Assembly of the triboelectric nanogenerator: the surfaces of the first amino acid composite material layer and the second amino acid composite material layer in the first friction layer and the second friction layer face inward, the first metal current collector layer and the second metal collector layer With the fluid layer facing outwards, the triboelectric nanogenerators were assembled in a vertical separation mode (with an interval of 1 mm), and then the output wires were led out. Its schematic diagram is shown in Figure 3.

Example 2

The present embodiment provides a fully degradable triboelectric nanogenerator, and its preparation method is as follows:

(1) Preparation of the first amino acid composite material layer: silk fibroin was added to a deionized aqueous solution, fully dissolved and centrifuged to remove impurities to obtain a silk fibroin aqueous solution with a mass fraction of 10%. Next, add lysine powder to the silk fibroin aqueous solution so that the mass ratio of serine and silk fibroin in the mixed solution is 0.35:1, and stir well. Finally, the obtained mixed solution was poured into a clean glass dish, left standing at 25°C to remove air bubbles, and then placed in a vacuum drying oven at 60°C for 18 hours to obtain a first amino acid composite material layer with a thickness of 800 μm.

(2) Preparation of the second amino acid composite material layer: firstly, the polyvinyl alcohol polymer material was added to the deionized aqueous solution, heated to 95° C. and fully stirred to obtain a polyvinyl alcohol aqueous solution with a mass fraction of 8%. Next, threonine powder is added to the polyvinyl alcohol solution to make the mass ratio of threonine and polyvinyl alcohol in the mixed solution to be 0.6:1, and the mixture is fully stirred. Finally, the obtained mixed solution was poured into a clean glass plate, left standing at 25°C to remove air bubbles, and then placed in a 60°C vacuum drying oven for 24 hours to obtain a second amino acid composite material layer with a thickness of 400 μm.

Since the composite material layer prepared above has good mechanical properties and can be used as a base layer at the same time, there is no need to prepare an additional base layer, and the composite material layer can be directly used in the friction layer structure.

(3) prepare the metal iron current collector layer by measuring and controlling sputtering on one side of the first amino acid composite material layer and the second amino acid composite material layer respectively, and the specific process is as follows: the composite material layer is placed on a magnetron sputtering apparatus In the cavity, sputtering parameters DC sputtering power 100W, duration 20min, obtain a first metal current collector layer and a second metal current collector layer with a thickness of 600nm, and simultaneously obtain a first friction layer and a second friction layer.

(4) Assembly of the triboelectric nanogenerator: the surfaces of the first amino acid composite material layer and the second amino acid composite material layer in the first friction layer and the second friction layer face inward, the first metal current collector layer and the second metal collector layer With the fluid layer facing outwards, the triboelectric nanogenerators were assembled in a vertical separation mode (with an interval of 2 mm), and then the output wires were led out.

Example 3

The present embodiment provides a fully degradable triboelectric nanogenerator, and its preparation method is as follows:

(1) Preparation of the first amino acid composite material layer: adding gelatin into a deionized aqueous solution, fully dissolving it, and centrifuging to remove impurities to obtain an aqueous gelatin solution with a mass fraction of 8%. Next, add glutamine powder to the gelatin aqueous solution so that the mass ratio of glutamine and gelatin in the mixed solution is 0.8:1, and stir well. Finally, the obtained mixed solution was poured into a clean glass plate, left standing at 25°C to remove air bubbles, and then placed in a vacuum drying oven at 40°C for 24 hours to obtain a first amino acid composite material layer with a thickness of 80 μm.

(2) Preparation of the second amino acid composite material layer: firstly, the polyethylene oxide polymer material was added to the deionized aqueous solution, heated to 90°C and fully stirred to obtain a polyethylene oxide aqueous solution with a mass fraction of 10%. Next, alanine powder was added to the polyethylene oxide solution to make the mass ratio of alanine and polyethylene oxide in the mixed solution to be 1.2:1, and the mixture was fully stirred. Finally, the obtained mixed solution was poured into a clean glass dish, left standing at 25°C to remove air bubbles, and then placed in a vacuum drying oven at 60°C for 24 hours to obtain a second amino acid composite material layer with a thickness of 1 mm.

Because the mechanical strength of the first amino acid composite material layer prepared above is relatively poor, it needs to be attached to the base layer and used as a friction layer structure.

(3) Weigh the polyethylene oxide polymer material and add it into the deionized aqueous solution, heat it to 90° C. and stir well to obtain a polyethylene oxide solution with a mass fraction of 10%. Then, the obtained mixed solution was poured into a clean glass plate, left standing at 25°C to remove air bubbles, and then placed in a vacuum drying oven at 60°C for 24 hours to obtain a PEO film base layer material. Finally the first amino acid composite layer is adhered to the PEO base layer.

(4) The metal molybdenum current collector layer is prepared by measuring and controlling sputtering on the side of the PEO base layer far away from the first amino acid composite material layer and the side of the second amino acid composite material layer in step (3) respectively, and the specific process is as follows : The composite material layer is placed in the cavity of the magnetron sputtering instrument, the sputtering parameter DC sputtering power is 100W, the duration is 20min, and the first metal current collector layer and the second metal current collector layer with a thickness of 700nm are obtained. A first friction layer and a second friction layer.

(5) Assembly of the triboelectric nanogenerator: the surfaces of the first amino acid composite material layer and the second amino acid composite material layer in the first friction layer and the second friction layer face inward, the first metal current collector layer and the second metal collector layer With the fluid layer facing outward, the triboelectric nanogenerators were assembled in a vertical separation mode (with an interval of 1.5 mm), and then the output wires were led out.

Evaluation test:

The electrical output performance of the triboelectric nanogenerators of Examples 1-3 is tested. The process is mainly to use a linear motor as an external force, set its operating frequency to 1HZ, and use a Teledyne LeCroy oscilloscope HDO9000 and Keithley ) electrometer 6517B to test the open-circuit voltage (V _OC ) and short-circuit current (I _SC ) of the triboelectric nanogenerator, respectively. The results are shown in Table 1: Table 1

group	Open Circuit Voltage (V OC )	Short circuit current (I SC )
Example 1	35V	0.40μA
Example 2	40V	0.45μA
Example 3	45V	0.48μA

It can be seen from the data in Table 1 that the fully degradable triboelectric nanogenerator involved in the present invention has very good electrical output performance, its open-circuit voltage can reach 35-45V, and its short-circuit current can reach 0.40-0.48μA, which are significantly higher than those of the present invention. There are technologies (such as literature S.Parandeh, M.Kharaziha, F.Karimzadeh, An eco-friendly triboelectric hybrid nanogenerators based on graphene oxide incorporated polycaprolactone fibers and cellulose paper, Nano Energy, Volume 59, 2019, Pages 412-421.) Triboelectric nanogenerators using PCL/GO and cellulose paper as the triboelectrode layer were disclosed at 20 V and 0.15 μA, respectively.

The applicant declares that the present invention illustrates a fully degradable triboelectric nanogenerator and its preparation method and application through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on Only the above-mentioned embodiment can be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

The preferred embodiments of the present invention are described in detail above, but the present invention is not limited to the specific details of the above-mentioned embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.

In addition, it should be noted that the specific technical features described in the above-mentioned specific embodiments can be combined in any suitable manner under the condition of no contradiction. In order to avoid unnecessary repetition, the present invention has The combination method will not be specified otherwise.

Claims (10)

1. A fully degradable triboelectric nanogenerator, characterized in that the fully degradable triboelectric nanogenerator comprises a first friction layer and a second friction layer; the first friction layer comprises first amino acid composite materials stacked in sequence layer and a first metal current collector layer; the second friction layer includes a second amino acid composite material layer and a second metal current collector layer stacked in sequence.
2. The fully degradable triboelectric nanogenerator according to claim 1, wherein the preparation raw materials of the first amino acid composite material layer include amino acids and/or amino acid derivatives, and also include polymer materials;

   The polymer materials include collagen, gelatin, soybean protein, egg white, silk fibroin, sodium alginate, cellulose, lignin, chitin, chitosan, hyaluronic acid, polyethylene oxide, polycaprolactone, poly Any one or a combination of at least two of lactic acid, polylactic acid-glycolic acid copolymer, polyvinyl alcohol, microbial polyester, polydioxanone or polyanhydride;

   Preferably, the mass ratio of the amino acid and/or amino acid derivative to the polymer material is (0.1-2.0):1.
3. The fully degradable triboelectric nanogenerator according to claim 1 or 2, wherein the preparation raw materials of the second amino acid composite material layer include amino acids and/or amino acid derivatives, and also include polymer materials;

   The polymer materials include collagen, gelatin, soybean protein, egg white, silk fibroin, sodium alginate, cellulose, lignin, chitin, chitosan, hyaluronic acid, polyethylene oxide, polycaprolactone, poly Any one or a combination of at least two of lactic acid, polylactic acid-glycolic acid copolymer, polyvinyl alcohol, microbial polyester, polydioxanone or polyanhydride;

   Preferably, the mass ratio of the amino acid and/or amino acid derivative to the polymer material is (0.1-2.0):1.
4. The fully degradable triboelectric nanogenerator according to any one of claims 1-3, wherein the first metal current collector layer and the second metal current collector layer are prepared from raw materials independently selected from magnesium, molybdenum , any one of tungsten or iron or a combination of at least two of them.
5. The fully degradable triboelectric nanogenerator according to any one of claims 1-4, wherein the first friction layer further comprises a layer overlapping the first amino acid composite material layer and the first metal current collector layer the first substrate layer;

   Preferably, the second friction layer further comprises a second base layer overlapping the second amino acid composite material layer and the second metal current collector layer;

   Preferably, the thickness of the first base layer is 10-5000 μm;

   Preferably, the thickness of the second base layer is 10-5000 μm;

   Preferably, the preparation materials of the first base layer and the second base layer are independently selected from collagen, gelatin, soybean protein, egg white, silk fibroin, sodium alginate, cellulose, lignin, chitin, chitosan , hyaluronic acid, polyethylene oxide, polycaprolactone, polylactic acid, polylactic acid-co-glycolic acid copolymer, polyvinyl alcohol, microbial polyester, polydioxanone or any one or at least one of polyanhydrides combination of the two.
6. The fully degradable triboelectric nanogenerator according to any one of claims 1-5, wherein the thicknesses of the first amino acid composite material layer and the second amino acid composite material layer are independently 1-5000 μm;

   Preferably, the thicknesses of the first metal current collector layer and the second metal current collector layer are independently 10 nm-10 μm.
7. The preparation method of the fully degradable triboelectric nanogenerator according to any one of claims 1-6, characterized in that, the preparation method comprises the steps of: the first friction layer and the second friction layer of the first friction layer The surfaces of the amino acid composite material layer and the second amino acid composite material layer face inward, and the first metal current collector layer and the second metal current collector layer face outward, and are assembled into the fully degradable triboelectric nanogenerator of vertical contact separation type.
8. The preparation method of the fully degradable triboelectric nanogenerator according to claim 7, wherein the preparation method of the first friction layer comprises the following steps:

   (1) mixing the preparation raw materials of the first amino acid composite material layer with a solvent, homogenizing, then casting film, spin coating, casting film or melting film, and drying to obtain the first amino acid composite material layer;

   (2) preparing the first metal current collector layer by electroplating, spraying or magnetron sputtering on one side of the first amino acid composite material layer, and finally obtaining the first friction layer;

   Preferably, the mass fraction of the homogenized polymer material is 1-20%;

   Preferably, the drying temperature is 40-80°C, and the drying time is 10-30h;

   Preferably, after the first amino acid composite material layer is obtained in step (1), it further includes step (1'): adhering the first base layer on one side of the first amino acid composite material layer; then on the first base layer away from the first base layer A first metal current collector layer is prepared on one side of the amino acid composite material layer by electroplating, spraying or magnetron sputtering, and finally the first friction layer is obtained;

   Preferably, the preparation method of the first base layer comprises: mixing the preparation raw materials of the first base layer with a solvent, homogenizing, then casting into a film, spin coating, casting into a film or melting into a film, and drying to obtain first base layer.
9. The preparation method of the fully degradable triboelectric nanogenerator according to claim 7, wherein the preparation method of the second friction layer comprises the following steps:

   (1) mixing the preparation raw material of the second amino acid composite material layer with a solvent, homogenizing, then casting into a film, spin coating, casting into a film or melting into a film, and drying to obtain a second amino acid composite layer;

   (2) the second metal current collector layer is prepared by the method of electroplating, spraying or magnetron sputtering on one side of the second amino acid composite material layer, and finally the second friction layer is obtained;

   Preferably, the mass fraction of the homogenized polymer material is 1-20%;

   Preferably, the drying temperature is 40-80°C, and the drying time is 10-30h;

   Preferably, after obtaining the second amino acid composite material layer in step (1), it further includes step (1'): adhering the second base layer on one side of the second amino acid composite material layer; A second metal current collector layer is prepared on one side of the diamino acid composite material layer by electroplating, spraying or magnetron sputtering, and finally the second friction layer is obtained;

   Preferably, the preparation method of the second base layer comprises: mixing the preparation raw materials of the second base layer with a solvent, homogenizing, then casting into a film, spin coating, casting into a film or melting into a film, and drying to obtain second base layer.
10. Application of the fully degradable triboelectric nanogenerator according to any one of claims 1 to 6 in energy supply for implantable medical devices.

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