CN114257117B - Amino acid gel electrode material friction nano generator and preparation method and application thereof - Google Patents

Amino acid gel electrode material friction nano generator and preparation method and application thereof Download PDF

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CN114257117B
CN114257117B CN202011003155.2A CN202011003155A CN114257117B CN 114257117 B CN114257117 B CN 114257117B CN 202011003155 A CN202011003155 A CN 202011003155A CN 114257117 B CN114257117 B CN 114257117B
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amino acid
acid gel
friction
electrode material
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CN114257117A (en
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江文
孙蓉
朱朋莉
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Shenzhen Institute of Advanced Technology of CAS
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    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
    • H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
    • H02N1/04—Friction generators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/04—Alginic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/04—Alginic acid; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/02—Polyalkylene oxides

Abstract

The invention relates to an amino acid gel electrode material friction nano-generator, a preparation method and application thereof, wherein the amino acid gel electrode material friction nano-generator comprises a first friction layer and a second friction layer; the first friction layer comprises a first amino acid gel material layer, a first basal layer and a first metal current collector layer which are sequentially overlapped; the second friction layer comprises a second amino acid gel material layer, a second basal layer and a second metal current collector layer which are sequentially overlapped. According to the invention, the amino acid gel material is used as the friction layer electrode material of the friction nano-generator, and the amino acid gel material with different functional group structures is selected as the friction layer electrode material, so that the electron gain and loss capability between friction layers is greatly differentiated, the purpose of effectively improving the electromechanical output performance of the friction nano-generator is achieved, and the electrical output performance is adjustable.

Description

Amino acid gel electrode material friction nano generator and preparation method and application thereof
Technical Field
The invention belongs to the technical field of medical equipment, relates to a friction nano-generator and a preparation method and application thereof, in particular to an amino acid gel electrode material friction nano-generator and a preparation method and application thereof, and especially relates to an amino acid gel electrode material friction nano-generator with high electric output performance and a preparation method and application thereof.
Background
Implantable medical devices (Implantable Medical Devices, IMDs for short) are now widely used in clinical medicine because of their flexibility and convenience in use, ability to monitor patient health in real time, and effective treatment of a variety of sudden conditions. Currently, the key factor limiting the development of active IMDs is mainly the energy supply problem. The vast majority of active IMDs are powered primarily by built-in batteries, which cease to function properly once the battery power is exhausted.
Tribo-nano generators (TENG) are a new energy harvesting technology developed in recent years that has been demonstrated to efficiently collect mechanical energy generated by tissue or organ movements in the body of an organism and convert it into electrical energy output. The electric energy output obtained by TENG conversion can charge the IMDs battery, which provides a brand new selection mode for IMDs power source.
Currently, electronic products continuously generate a large amount of electronic waste (E-waste) worldwide each year due to update, breakage, and the like. These waste electronic waste often contains a large amount of toxic and harmful metallic or nonmetallic elements, and conventional landfill and incineration treatment methods have disastrous consequences for the human living environment such as water sources, land, air and the like. Therefore, development of novel materials which are low in toxicity, environment-friendly, renewable and degradable to replace part of components of the current electronic products or to prepare novel electronic equipment with completely zero waste emission is a 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 immediately or completely disappeared under the triggering of external stimulus. The occurrence of transient electronic technology can greatly improve the serious E-waste pollution problem generated after the electronic product is scrapped in the traditional sense.
The transient electronic technology is applied to the field of IMDs, after the device finishes the use function, degradation can occur in organisms and is metabolized or absorbed by human bodies, and a patient can avoid performing a secondary operation to remove the device, so that the pain of the patient is greatly relieved, the potential operation risk and inflammatory reaction are reduced, the medical cost is reduced, and the medical resource waste is prevented.
The electrical output performance of a triboelectric nano-generator is largely dependent on the amount of charge transfer between the triboelectric layer materials, which is closely related to the molecular composition of the materials constituting the triboelectric layer surface, with molecules having different functional groups exhibiting different electron gain and loss capacities. The friction layer materials selected by the full-degradable friction nano generator at present have single composition, so that the electron gain and loss capability among the friction layers are similar or the same, and the transferred charge quantity is low, and the electromechanical output performance of the friction nano generator is low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a friction nano-generator and a preparation method and application thereof, in particular to an amino acid gel electrode material friction nano-generator and a preparation method and application thereof, and especially provides an amino acid gel electrode material friction nano-generator with high electric output performance and a preparation method and application thereof.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an amino acid gel electrode material friction nanogenerator comprising a first friction layer and a second friction layer; the first friction layer comprises a first amino acid gel material layer, a first basal layer and a first metal current collector layer which are sequentially overlapped; the second friction layer comprises a second amino acid gel material layer, a second basal layer and a second metal current collector layer which are sequentially overlapped.
According to the invention, the amino acid gel material is used as the friction layer electrode material of the friction nano-generator, and the amino acid gel material with different functional group structures is selected as the friction layer electrode material, so that the electron gain and loss capability between friction layers is greatly differentiated, and the purpose of effectively improving the electromechanical output performance of the friction nano-generator is achieved. Meanwhile, the invention also provides an amino acid gel material which is used as a friction layer electrode material of the friction nano generator for the first time, and the invention is a novel implantable full-degradable friction nano generator structure.
Preferably, the preparation raw materials of the first amino acid gel material layer and the second amino acid gel material layer are independently selected from at least one amino acid derivative. Namely, the first amino acid gel material layer or the second amino acid gel material layer can be prepared from one amino acid derivative or can be prepared by compounding two or more amino acid derivatives, and the effect of the latter on improving the electrical output performance of the friction nano-generator is more remarkable.
Preferably, the amino acid derivative is an amino acid derivative capable of self-assembling to form a gel.
Amino acids modified with 9-fluorenylmethoxycarbonyl, naphthyl, benzyl, or budinaphthyl, for example, 9-fluorenylmethoxycarbonyl-tyrosine (Fmoc-Tyr), pentafluorobenzyl-phenylalanine, 9-fluorenylmethoxycarbonyl-phenylalanine (Fmoc-Phe), 9-fluorenylmethoxycarbonyl-pentafluoro-phenylalanine (Fmoc-F) 5 Phe), bezitane-serine (Pyr-Ser), and the like.
Preferably, the thickness of the first amino acid gel material layer and the second amino acid gel material layer is independently 1 μm-5mm, for example, 1 μm, 10 μm, 50 μm, 100 μm, 200 μm, 500 μm, 800 μm, 1000 μm, 2000 μm or 5000 μm, etc., and other specific values within the above numerical ranges are selected, and will not be described in detail herein.
Preferably, the preparation raw materials of the first substrate layer and the second substrate layer are independently selected from any one or a combination of at least two of collagen, gelatin, soy protein, egg white, silk fibroin, sodium alginate, cellulose, lignin, chitin, chitosan, hyaluronic acid, polyglycolide, polycaprolactone, polylactic acid-glycolic acid copolymer, polyvinyl alcohol, microbial polyester, polydioxanone, polyethylene oxide, polytrimethylene carbonate, polysebacic acid glycerol ester or polyanhydride.
The preparation raw materials of the first basal layer and the second basal layer are high polymer materials with good biocompatibility and biological absorbability, so that the prepared nano generator not only has full degradability, but also can be implanted in a living body.
The combination of at least two of the above-mentioned components, such as a combination of egg white and silk fibroin, a combination of sodium alginate and cellulose, a combination of chitosan and hyaluronic acid, etc., may be selected, and any other combination manner will not be described here.
Preferably, the thickness of the first substrate layer and the second substrate layer is independently 10 μm-5mm, for example, 10 μm, 50 μm, 100 μm, 200 μm, 500 μm, 800 μm, 1000 μm, 2000 μm, 3000 μm, 4000 μm, 45000 μm or 5000 μm, etc., and other specific values within the above numerical ranges are selected, and will not be described in detail herein.
Preferably, the first metal current collector layer and the second metal current collector layer are prepared from any one or a combination of at least two of magnesium, molybdenum, tungsten or iron.
The combination of at least two of the above-mentioned compounds, such as a combination of magnesium and molybdenum, a combination of molybdenum and tungsten, a combination of tungsten and iron, etc., may be selected in any other combination manner, and will not be described in detail herein.
Preferably, the thickness of the first metal current collector layer and the second metal current collector layer is independently 10nm-10 μm, for example, 10nm, 50nm, 100nm, 200nm, 500nm, 800nm, 1 μm, 2 μm, 5 μm, 6 μm, 8 μm or 10 μm, etc., and other specific values within the above numerical ranges are selected, and will not be described in detail herein.
Preferably, the amino acid gel electrode material friction nano-generator further comprises a first packaging layer and a second packaging layer; the first packaging layer is laminated on one side of the first amino acid gel material layer far away from the first basal layer; the second packaging layer is laminated on one side of the second amino acid gel material layer far away from the second basal layer.
Preferably, the preparation raw materials of the first encapsulation layer and the second encapsulation layer are independently selected from any one or a combination of at least two of collagen, gelatin, soy protein, egg white, silk fibroin, sodium alginate, cellulose, lignin, chitin, chitosan, hyaluronic acid, polyglycolide, polycaprolactone, polylactic acid-glycolic acid copolymer, polyvinyl alcohol, microbial polyester, polydioxanone, polyethylene oxide, polytrimethylene carbonate, polysebacic acid glycerol ester or polyanhydride.
The preparation raw materials of the first packaging layer and the second packaging layer are high polymer materials with good biocompatibility and biological absorbability, so that the prepared nano generator not only has full degradability, but also can be implanted in a living body.
The combination of at least two of the above-mentioned components, such as a combination of collagen and gelatin, a combination of silk fibroin and sodium alginate, a combination of cellulose and lignin, etc., may be selected in any other combination manner, and will not be described in detail herein.
Preferably, the thickness of the first packaging layer and the second packaging layer is independently 10 μm-5mm, for example, 10 μm, 50 μm, 100 μm, 200 μm, 500 μm, 800 μm, 1mm, 2mm, 4mm or 5mm, and other specific values within the above numerical ranges may be selected, and will not be described in detail here.
When the thicknesses of all layers in the friction generator disclosed by the invention meet the numerical range, the manufactured friction generator has more remarkable effect of improving the electric output performance.
In a second aspect, the present invention provides a method for preparing the friction nano-generator made of the amino acid gel electrode material according to the first aspect, the method comprising the following steps: and the surfaces of the first amino acid gel material layer and the second amino acid gel material layer in the first friction layer and the second friction layer are inwards, and the first metal current collector layer and the second metal current collector layer are outwards, so that the vertical contact separation type amino acid gel electrode material friction nano generator 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., and other specific point values in the above numerical ranges can be selected, so that details are not repeated here.
Preferably, the preparation method of the first friction layer comprises the following steps:
(1) Performing self-assembly gelation reaction on the preparation raw materials of the first amino acid gel material layer to obtain gel, transferring the gel to one side of a first basal layer, and drying to obtain a first electrode layer;
the preparation method of the first substrate layer comprises the following steps: mixing the preparation raw materials of the first substrate layer with a solvent, homogenizing, then casting to form a film, rotating to form a film, casting to form a film or fusing to form a film, and drying to obtain the first substrate layer;
(2) And preparing a first metal current collector layer on one side of the first basal layer far away from the first amino acid gel material layer by an electroplating, spraying or magnetron sputtering method, and finally obtaining the first friction layer.
Preferably, the preparation method of the second friction layer comprises the following steps:
(1) Performing self-assembly gelation reaction on the preparation raw materials of the second amino acid gel material layer to obtain gel, transferring the gel to one side of a second substrate layer, and drying to obtain a second electrode layer;
the preparation method of the second substrate layer comprises the following steps: mixing the preparation raw materials of the second substrate layer with a solvent, homogenizing, then casting to form a film, rotating to form a film, casting to form a film or fusing to form a film, and drying to obtain the second substrate layer;
(2) And preparing a second metal current collector layer on one side of the second basal layer far away from the first amino acid gel material layer by electroplating, spraying or magnetron sputtering to finally obtain the second friction layer.
Preferably, the amino acid gel electrode material is packaged after being assembled by friction nano generator, and the packaging method comprises the following steps:
placing a packaging layer on one side of the amino acid gel electrode material friction nano generator, wherein the friction nano generator is positioned in the middle position of the packaging layer; and placing another packaging layer with the same size on the other side of the amino acid gel electrode material friction nano generator, and enabling the peripheries of the two packaging layers to be overlapped and sealed.
In a third aspect, the present invention provides the use of an amino acid gel electrode material friction nano-generator according to the first aspect for energy supply for implantable medical devices.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts amino acid gel material as the electrode material of the friction layer of the friction nano-generator, and has different functions by selectingThe amino acid gel material with the group structure is used as the electrode material of the friction layer, so that the electron gain and loss capability between the friction layers is greatly differentiated, and the aim of effectively improving the electric output performance of the friction nano-generator is fulfilled. Its open circuit voltage (V) OC ) Up to 65V, its short-circuit current (I SC ) Up to 0.80 mua, and this electrical output performance is adjustable. The invention provides an amino acid gel material as a friction layer electrode material of a friction nano generator for the first time, which is a novel implantable full-degradable friction nano generator structure.
Drawings
FIG. 1 is a schematic view of the first electrode layer or the second electrode layer prepared in example 1, 11 is a first amino acid gel material layer or a second amino acid gel material layer, and 12 is a first base layer or a second base layer;
fig. 2 is a schematic view of the first friction layer or the second friction layer prepared in example 1, 11 is a first amino acid gel material layer or a second amino acid gel material layer, 12 is a first base layer or a second base layer, and 13 is a first metal current collector layer or a second metal current collector layer;
fig. 3 is a schematic view of the friction nano-generator prepared in example 1, 11 is a first amino acid gel material layer or a second amino acid gel material layer, 12 is a first base layer or a second base layer, and 13 is a first metal current collector layer or a second metal current collector layer;
fig. 4 is a schematic diagram of the packaged friction nano-generator made in example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The sources of the polymeric materials involved in the following examples are as follows:
PCL was purchased from Sigma-Aldrich under the designation viscosity1.5dL/g.
Sodium alginate was purchased from Sigma-Aldrich under the model of viscosityity 15-25cP,1% in H 2 O。
9-fluorenylmethoxycarbonyl-phenylalanine (Fmoc-Phe) was purchased from Bachem.
9-fluorenylmethoxycarbonyl-pentafluoro-phenylalanine (Fmoc-F) 5 Phe) from Bachem.
PLGA was purchased from Jinan Dai, biological engineering Co., ltd., model number 8.8-11.7 (ten thousand).
PVA was purchased from Sigma-Aldrich under the model of average M w 130000。
9-fluorenylmethoxycarbonyl-tyrosine (Fmoc-Tyr) was purchased from Bachem.
Pentafluorobenzyl-phenylalanine was purchased from Bachem.
PTMC was purchased from Jinan Dai, inc. of biological engineering Co., ltd. And model number was 11.8-19.8 (ten thousand).
PEO was purchased from Sigma-Aldrich under the model average M v 200000。
In naphthalene-serine (Pyr-Ser) was purchased from Bachem.
Fmoc-F 5 Phe-OH was purchased from Bachem.
Fmoc-F 5 -Phe-NH 2 Available from Bachem.
Example 1
The embodiment provides an amino acid gel electrode material friction nano generator, which is prepared by the following steps:
(1) Preparation of the first substrate layer: PCL (polycaprolactone) polymer material is dissolved in dichloromethane solution, and is stirred uniformly to form a homogeneous solution with the mass fraction of 10%. Adding the PCL solution into a clean glass plate, standing at 25 ℃ to remove bubbles, and then placing the plate in a vacuum drying oven at 80 ℃ for 12 hours to obtain a first basal layer with the thickness of 400 mu m;
(2) Preparation of the second substrate layer: firstly, preparing an acetic acid solution with the volume fraction of 1%, then adding sodium alginate powder material into the acetic acid solution, and uniformly stirring to form a homogeneous solution with the mass fraction of 5%. Adding the sodium alginate solution into a clean glass plate, standing at 25 ℃ to remove bubbles, and then placing in a vacuum drying oven at 60 ℃ for 24 hours to obtain a second basal layer with the thickness of 400 mu m;
(3) Preparation of the first electrode layer: 9-fluorenylmethoxycarbonyl-phenylalanine (Fmoc-Phe) frozen powder was dissolved in sodium carbonate solution (0.1M), and deionized water solution was added to form a homogeneous solution with a mass-volume fraction of 20 mg/mL. Slowly heating to 90 ℃, cooling at 25 ℃ and standing to obtain the gel material. Transferring the gel onto the prepared first substrate layer, standing at 25 ℃ and naturally drying for 24 hours to obtain a first electrode layer with the thickness of 450 mu m; a schematic diagram thereof is shown in fig. 1;
(4) Preparation of a second electrode layer: 9-fluorenylmethoxycarbonyl-pentafluoro-phenylalanine (Fmoc-F) 5 Phe) frozen powder was dissolved in absolute ethanol solution to form a homogeneous solution with a mass-volume fraction of 10 mg/mL. And then adding a certain amount of deionized water solution into the solution to obtain a final solution with the mass volume fraction of 5mg/mL, and standing at 25 ℃ to obtain the gel material. Transferring the gel onto the prepared second substrate layer, standing at 25 ℃ and naturally drying for 48 hours to obtain a second electrode layer with the thickness of 440 mu m; a schematic diagram thereof is shown in fig. 1;
(5) The metal magnesium current collector layers (respectively forming a first current collector layer on the first electrode layer and a second current collector layer on the second electrode layer) are prepared on the sides of the first substrate layer and the second substrate layer far away from gel by a measurement and control sputtering method, and the specific process is as follows: placing one end of the electrode layer gel downwards in a cavity of a magnetron sputtering instrument, wherein the sputtering parameter is that the direct current sputtering power is 100W, the duration time is 25min, a first metal current collector layer and a second metal current collector layer with the thickness of 600nm are obtained, and meanwhile, a first friction layer and a second friction layer are obtained, and the schematic diagram is shown in figure 2;
(6) Assembling a friction nano generator: the first amino acid gel material layer and the second amino acid gel material layer in the first friction layer and the second friction layer are arranged with the surfaces facing inwards, the first metal current collector layer and the second metal current collector layer facing outwards, and the friction nano generator (with a space of 1 mm) is assembled by a vertical separation mode, and then an output wire is led out, wherein a schematic diagram is shown in figure 3;
(7) Packaging of the friction nano generator: placing a packaging layer on one side of the amino acid gel electrode material friction nano generator, wherein the friction nano generator is positioned in the middle position of the packaging layer; and placing another packaging layer with the same size on the other side of the amino acid gel electrode material friction nano generator, and enabling the peripheries of the two packaging layers to be overlapped and sealed. A schematic diagram thereof is shown in fig. 4. The packaging layer is made of PCL material, and the preparation method of the packaging layer is the same as that of the first basal layer.
Example 2
The embodiment provides an amino acid gel electrode material friction nano generator, which is prepared by the following steps:
(1) Preparation of the first substrate layer: PLGA polymer material is dissolved in dichloromethane solution and stirred uniformly to form homogeneous solution with mass fraction of 10%. Adding the PLGA solution into a clean glass plate, standing at 25 ℃ to remove bubbles, and then placing in a vacuum drying oven at 80 ℃ for 12 hours to obtain a first basal layer with the thickness of 500 mu m;
(2) Preparation of the second substrate layer: adding PVA material into deionized water, heating and stirring uniformly to form a homogeneous solution with the mass fraction of 8%. Adding the PVA solution into a clean glass plate, standing at 25 ℃ to remove bubbles, and then placing the plate in a vacuum drying oven at 80 ℃ for 24 hours to obtain a second substrate layer with the thickness of 600 mu m;
(3) Preparation of the first electrode layer: 9-fluorenylmethoxycarbonyl-tyrosine (Fmoc-Tyr) frozen powder was dissolved in a dimethyl sulfoxide (DMSO) solution to form a homogeneous solution having a mass volume fraction of 100 mg/mL. And then adding a certain amount of deionized water solution into the original solution to obtain a final solution with the mass volume fraction of 5mg/mL, and standing at 25 ℃ to obtain the gel material. Transferring the gel onto the prepared first substrate layer, standing at 25 ℃ and naturally drying for 48 hours to obtain a first electrode layer with the thickness of 670 mu m;
(4) Preparation of a second electrode layer: and dissolving the pentafluorobenzyl-phenylalanine frozen powder in deionized water solution, adding sodium hydroxide solution, and performing ultrasonic treatment to form a homogeneous solution with the mass fraction of 1%. And then hydrochloric acid solution is added dropwise into the solution to adjust the pH of the solution to 5, and the solution is kept stand at 25 ℃ to obtain the gel material. Transferring the gel onto the prepared second substrate layer, standing at 25 ℃ and naturally drying for 48 hours to obtain a second electrode layer with the thickness of 650 mu m;
(5) The metal iron current collector layers (respectively forming a first current collector layer on the first electrode layer and a second current collector layer on the second electrode layer) are prepared on the sides of the first substrate layer and the second substrate layer far away from gel by a measurement and control sputtering method, and the specific process is as follows: placing one end of the electrode layer gel downwards in a cavity of a magnetron sputtering instrument, wherein the sputtering parameter is that the direct current sputtering power is 100W, the duration time is 25min, a first metal current collector layer and a second metal current collector layer with the thickness of 600nm are obtained, and a first friction layer and a second friction layer are obtained simultaneously;
(6) Assembling a friction nano generator: the method comprises the steps of (1) assembling a friction nano generator (with a spacing of 2 mm) in a vertical separation mode by enabling the surfaces of a first amino acid gel material layer and a second amino acid gel material layer in a first friction layer and a second friction layer to face inwards and enabling a first metal current collector layer and a second metal current collector layer to face outwards, and then leading out an output wire;
(7) Packaging of the friction nano generator: placing a packaging layer on one side of the amino acid gel electrode material friction nano generator, wherein the friction nano generator is positioned in the middle position of the packaging layer; and placing another packaging layer with the same size on the other side of the amino acid gel electrode material friction nano generator, and enabling the peripheries of the two packaging layers to be overlapped and sealed. The packaging layer is made of PVA material, and the preparation method of the packaging layer is the same as that of the first substrate layer.
Example 3
The embodiment provides an amino acid gel electrode material friction nano generator, which is prepared by the following steps:
(1) Preparation of the first substrate layer: and dissolving the PTMC polymer material in a dichloromethane solution, and uniformly stirring to form a homogeneous solution with the mass fraction of 15%. Adding the PTMC solution into a clean glass plate, standing at 25 ℃ to remove bubbles, and then placing the plate in a vacuum drying oven at 80 ℃ for 12 hours to obtain a first basal layer with the thickness of 700 mu m;
(2) Preparation of the second substrate layer: adding PEO material into deionized water, heating and stirring uniformly to form a homogeneous solution with the mass fraction of 10%. Adding the PEO solution into a clean glass plate, standing at 25 ℃ to remove bubbles, and then placing the plate in a vacuum drying oven at 80 ℃ for 24 hours to obtain a second basal layer with the thickness of 650 mu m;
(3) Preparation of the first electrode layer: the frozen powder of the embedded dinaphthyl-serine (Pyr-Ser) is dissolved in the redistilled water solution, and then 1M sodium hydroxide solution is added, and a clear solution is formed after ultrasonic treatment. Then, 1M sodium hydroxide solution and 1M sodium dihydrogen phosphate solution were added to the solution to form 100mM phosphate buffer solution. Finally, the pH of the solution is regulated to 6.5 by a method of dropwise adding 1M hydrochloric acid solution into the solution to obtain the gel material. Transferring the gel onto the prepared first substrate layer, heating and drying in a vacuum drying oven at 50 ℃ for 12 hours to obtain a first electrode layer with the thickness of 750 mu m;
(4) Preparation of a second electrode layer: fmoc-F weighed in a mass ratio of 1:1 5 Phe-OH and Fmoc-F 5 -Phe-NH 2 The amino acid derivative frozen powder was dissolved in dimethyl sulfoxide solution to form a 0.123M homogeneous solution. Deionized water solution was then added to form a homogeneous solution of 2.5 mM. Standing at 25 ℃ to obtain the gel material. Transferring the gel onto the prepared second substrate layer, heating and drying in a vacuum drying oven at 40 ℃ for 24 hours to obtain a second electrode layer with the thickness of 660 mu m;
(5) The metal molybdenum current collector layers (respectively forming a first current collector layer on the first electrode layer and a second current collector layer on the second electrode layer) are prepared on the sides of the first substrate layer and the second substrate layer far away from gel by a measurement and control sputtering method, and the specific process is as follows: placing one end of the electrode layer gel downwards in a cavity of a magnetron sputtering instrument, wherein the sputtering parameter is that the direct current sputtering power is 100W, the duration time is 25min, a first metal current collector layer and a second metal current collector layer with the thickness of 600nm are obtained, and a first friction layer and a second friction layer are obtained simultaneously;
(6) Assembling a friction nano generator: the method comprises the steps of (1) assembling a friction nano generator (with a space of 1.5 mm) in a vertical separation mode by enabling the surfaces of a first amino acid gel material layer and a second amino acid gel material layer in a first friction layer and a second friction layer to face inwards and enabling a first metal current collector layer and a second metal current collector layer to face outwards, and then leading out an output wire;
(7) Packaging of the friction nano generator: placing a packaging layer on one side of the amino acid gel electrode material friction nano generator, wherein the friction nano generator is positioned in the middle position of the packaging layer; and placing another packaging layer with the same size on the other side of the amino acid gel electrode material friction nano generator, and enabling the peripheries of the two packaging layers to be overlapped and sealed. The packaging layer is made of PTMC material, and the preparation method of the packaging layer is the same as that of the first substrate layer.
Evaluation test:
the electrical output performance of the friction nano-generators before encapsulation of examples 1-3 was tested by mainly using a linear motor as an external force, setting the operating frequency to 1HZ, and testing the open circuit voltage (V) characterizing the friction nano-generators by a force (Teledyne LeCroy) oscilloscope HDO9000 and a gizzard-ril (Keithley) electrometer 6517B, respectively OC ) And short-circuit current (I) SC ) Size of the product. The results are shown in Table 1:
TABLE 1
As can be seen from the data in table 1: the friction Nano generator of the amino acid gel electrode material has very good electric output performance, the open-circuit voltage can reach 55-65V, the short-circuit current can reach 0.65-0.80 mu A, and the friction Nano generator is remarkably higher than the friction Nano generator which respectively uses PCL/GO and cellulose paper as friction electrode layers in the prior art (such as document 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), and the open-circuit voltage is 20V and 0.15 mu A.
The applicant states that the present invention is described by the above examples as an amino acid gel electrode material friction nano-generator, and a preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.

Claims (16)

1. The amino acid gel electrode material friction nano generator is characterized by comprising a first friction layer and a second friction layer; the first friction layer comprises a first amino acid gel material layer, a first basal layer and a first metal current collector layer which are sequentially overlapped; the second friction layer comprises a second amino acid gel material layer, a second basal layer and a second metal current collector layer which are sequentially overlapped;
the amino acid gel electrode material friction nano generator is prepared by a preparation method comprising the following steps: and the surfaces of the first amino acid gel material layer and the second amino acid gel material layer in the first friction layer and the second friction layer are inwards, and the first metal current collector layer and the second metal current collector layer are outwards, so that the vertical contact separation type amino acid gel electrode material friction nano generator is assembled.
2. The amino acid gel electrode material friction nano-generator according to claim 1, wherein the first amino acid gel material layer and the second amino acid gel material layer are prepared from materials independently selected from at least one amino acid derivative.
3. The amino acid gel electrode material friction nano-generator of claim 2, wherein the amino acid derivative is an amino acid derivative capable of self-assembling to form a gel.
4. The amino acid gel electrode material friction nano-generator of claim 1, wherein the first amino acid gel material layer and the second amino acid gel material layer independently have a thickness of 1 μm-5mm.
5. The amino acid gel electrode material friction nano-generator according to claim 1, wherein the first substrate layer and the second substrate layer are prepared from any one or a combination of at least two of collagen, gelatin, soy protein, egg white, silk fibroin, sodium alginate, cellulose, lignin, chitin, chitosan, hyaluronic acid, polyglycolide, polycaprolactone, polylactic acid-glycolic acid copolymer, polyvinyl alcohol, microbial polyester, polydioxanone, polyethylene oxide, polytrimethylene carbonate, polysebacic acid glycerol ester, or polyanhydride.
6. The amino acid gel electrode material friction nano-generator of claim 1, wherein the first and second substrate layers independently have a thickness of 10 μιη -5mm.
7. The amino acid gel electrode material friction nano-generator according to claim 1, wherein the first metal current collector layer and the second metal current collector layer are prepared from raw materials independently selected from any one or a combination of at least two of magnesium, molybdenum, tungsten or iron.
8. The amino acid gel electrode material friction nano-generator of claim 1, wherein the thickness of the first metal current collector layer and the second metal current collector layer are independently 10nm-10 μm.
9. The amino acid gel electrode material friction nano-generator of claim 1, further comprising a first encapsulation layer and a second encapsulation layer; the first packaging layer is laminated on one side of the first amino acid gel material layer far away from the first basal layer; the second packaging layer is laminated on one side of the second amino acid gel material layer far away from the second basal layer.
10. The amino acid gel electrode material friction nano-generator according to claim 9, wherein the first and second encapsulation layers are prepared from any one or a combination of at least two of collagen, gelatin, soy protein, egg white, silk fibroin, sodium alginate, cellulose, lignin, chitin, chitosan, hyaluronic acid, polyglycolide, polycaprolactone, polylactic acid-glycolic acid copolymer, polyvinyl alcohol, microbial polyester, polydioxanone, polyethylene oxide, polytrimethylene carbonate, polysebacic acid glycerol ester, or polyanhydride.
11. The amino acid gel electrode material friction nano-generator of claim 9, wherein the thickness of the first encapsulation layer and the second encapsulation layer are independently 10 μm-5mm.
12. The method for preparing the amino acid gel electrode material friction nano-generator according to any one of claims 1 to 11, wherein the preparation method comprises the following steps: and the surfaces of the first amino acid gel material layer and the second amino acid gel material layer in the first friction layer and the second friction layer are inwards, and the first metal current collector layer and the second metal current collector layer are outwards, so that the vertical contact separation type amino acid gel electrode material friction nano generator is assembled.
13. The method for preparing the amino acid gel electrode material friction nano-generator according to claim 12, wherein the method for preparing the first friction layer comprises the following steps:
(1) Performing self-assembly gelation reaction on the preparation raw materials of the first amino acid gel material layer to obtain gel, transferring the gel to one side of a first basal layer, and drying to obtain a first electrode layer;
the preparation method of the first substrate layer comprises the following steps: mixing the preparation raw materials of the first substrate layer with a solvent, homogenizing, then casting to form a film, rotating to form a film, casting to form a film or fusing to form a film, and drying to obtain the first substrate layer;
(2) And preparing a first metal current collector layer on one side of the first basal layer far away from the first amino acid gel material layer by an electroplating, spraying or magnetron sputtering method, and finally obtaining the first friction layer.
14. The method for preparing the amino acid gel electrode material friction nano-generator according to claim 12, wherein the method for preparing the second friction layer comprises the following steps:
(1) Performing self-assembly gelation reaction on the preparation raw materials of the second amino acid gel material layer to obtain gel, transferring the gel to one side of a second substrate layer, and drying to obtain a second electrode layer;
the preparation method of the second substrate layer comprises the following steps: mixing the preparation raw materials of the second substrate layer with a solvent, homogenizing, then casting to form a film, rotating to form a film, casting to form a film or fusing to form a film, and drying to obtain the second substrate layer;
(2) And preparing a second metal current collector layer on one side of the second basal layer far away from the first amino acid gel material layer by electroplating, spraying or magnetron sputtering to finally obtain the second friction layer.
15. The method for preparing the amino acid gel electrode material friction nano-generator according to claim 12, wherein the amino acid gel electrode material friction nano-generator is packaged after being assembled, and the packaging method comprises the following steps:
placing a packaging layer on one side of the amino acid gel electrode material friction nano generator, wherein the friction nano generator is positioned in the middle position of the packaging layer; and placing another packaging layer with the same size on the other side of the amino acid gel electrode material friction nano generator, and enabling the peripheries of the two packaging layers to be overlapped and sealed.
16. Use of an amino acid gel electrode material friction nano-generator according to any one of claims 1-11 for energy supply for implantable medical devices.
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