Preparation and application method of friction nano-generator core friction layer used in wide-temperature-range extreme environment

Abstract

The invention discloses a preparation and application method of a friction nano-generator core friction layer used in a wide-temperature-range extreme environment, and relates to the technical field of nano-energy. And a novel friction layer material which can tolerate extreme temperature and different air pressures can be prepared, so that the prepared friction nano generator can efficiently and stably work for a long time under wide-temperature-range extreme conditions. According to the technical scheme, the core friction layer is a ternary composite film formed by compounding a polymer, natural minerals and a carbon-based nano material and then carrying out high-energy laser irradiation surface state regulation and control treatment on the compounded polymer, natural minerals and the carbon-based nano material; wherein the mass ratio of the high-temperature-resistant polymer to the natural mineral to the carbon-based nano material is 1: (0.12-0.50): (0.01-0.18). The friction nano-generator prepared from the friction layer material solves the problem that the performance of a traditional friction nano-generator is degraded or even completely invalid in a wide-temperature-range extreme environment, the application field is widened, a new scheme is provided for energy collection in the extreme environment, and the purpose of the invention is achieved.

Description

Technical Field

[0001] The present invention relates to the field of nano energy technology, and in particular to a method for preparing a core friction layer of a friction nanogenerator used in extreme environments over a wide temperature range. Background Art

[0002] The core friction layer inside the friction nanogenerator is usually made of polymer materials, such as polytetrafluoroethylene, polyvinylidene fluoride, etc. Although these materials exhibit good performance under normal conditions, their tolerance is still far from enough when faced with extreme environmental challenges, such as high temperature, low temperature, high pressure or low pressure and other extreme temperature and air pressure conditions.

[0003] Specifically, under the above extreme conditions, especially the high temperature, these materials can easily undergo significant changes in physical properties, such as thermal expansion, embrittlement, softening or structural damage, which can lead to a decrease in the performance of the friction layer or even complete failure. In addition, even if the intrinsic state of the material does not change much, the high temperature effect in the extreme environment will cause thermal electron emission on the surface of the friction layer, which will significantly reduce the power of the friction nanogenerator and even make it almost impossible to generate electricity. These problems have become the main bottleneck restricting the application of friction nanogenerators in extreme environments, greatly limiting their development potential in high-tech fields such as aerospace, deep-sea exploration, and polar scientific research.

[0004] As of now, people have not yet developed a friction nanogenerator that can be used for a long time in extreme environments of -40~200℃ and 0.1~20 standard atmospheres and operate stably.

[0005] Therefore, if a suitable new friction layer material can be invented so that the friction nanogenerator can be used in the above-mentioned wide temperature range extreme environment and maintain structural stability and functional reliability, it will be conducive to the further expansion of the application field of the friction nanogenerator and have very great application value and economic benefits. Summary of the invention

[0006] In response to the above problems, the present invention proposes a method for preparing the core friction layer of a friction nanogenerator for use in extreme environments with a wide temperature range. The method is capable of preparing a new friction layer material that can withstand extreme temperatures and different air pressures, thereby ensuring that the prepared friction nanogenerator can operate efficiently, stably and for a long time under extreme conditions with a wide temperature range.

[0007] The technical solution of the present invention is: the core friction layer is a ternary composite film formed by a polymer, a natural mineral, and a carbon-based nanomaterial composite and subjected to a surface state regulation treatment by high-energy laser irradiation; wherein the mass ratio of the high-temperature resistant polymer, the natural mineral, and the carbon-based nanomaterial is 1:0.12~0.50:0.01~0.18; The core friction layer is prepared according to the following steps: Step 1: Take natural minerals, wash and dry them; Soak the natural mineral in the cleaning solution, perform ultrasonic cleaning for 5 to 20 minutes, then rinse it with deionized water, and then put it in an oven to dry at 60 to 150°C for 0.5 to 5 hours.

[0008] Step 2, modifying the natural minerals; Soak the cleaned natural mineral in the modified liquid, stir for 5 to 50 minutes, take it out and dry it at 80 to 150°C for 0.2 to 8 hours.

[0009] Step 3, taking the carbon-based nanomaterial and performing oxidation treatment; First, the carbon-based nanomaterials are mixed with the oxidant, and then reacted at a temperature of 20-80°C for 1-12 hours, followed by washing with deionized water and finally drying at a temperature of 60-80°C.

[0010] Step 4: taking a high temperature resistant polymer, compounding it with the modified natural mineral and the oxidized carbon-based nanomaterial to form a polymer / natural mineral / carbon-based nanomaterial ternary composite film; The mass ratio of high temperature resistant polymer, natural mineral and carbon-based nanomaterial is 1:0.12~0.50:0.01~0.18; Among them, the high temperature resistant polymer is a thermosetting polymer or a thermoplastic polymer; in particular, when the high temperature resistant polymer is a thermosetting polymer, a commercial thermosetting polymer precursor is usually required. Considering that there are other components such as solvents, its mass is measured by the content of the thermosetting polymer therein.

[0011] When the high temperature resistant polymer is a thermosetting polymer, the composite method of the thermosetting polymer, the natural mineral and the carbon-based nanomaterial is as follows: adding the modified natural mineral and the oxidized carbon-based nanomaterial to the thermosetting polymer precursor, stirring at high speed for 5 to 60 minutes, then pouring the solution into a mold with a flat bottom, and drying at room temperature for 5 to 20 hours to form a film; then freeze-drying the film at a temperature of -50 to -20°C, an air pressure of 0.1 to 10Pa, and keeping warm for 5 to 40 hours; then curing at 80 to 400°C for 0.5 to 4 hours under a protective atmosphere, and the prepared film has a thickness of 0.01 to 3 mm; When the high temperature resistant polymer is a thermoplastic polymer, the composite method of the thermoplastic polymer, natural minerals and carbon-based nanomaterials is as follows: at a temperature of 220~400°C, the modified natural minerals and the oxidized carbon-based nanomaterials are added to the thermoplastic polymer and mechanically mixed for 10~30 minutes; after cooling, the mixture is placed in a hot press at a temperature of 250~450°C and a pressure of 5~10MPa for 5~15 minutes; finally, a film is obtained after cooling to room temperature with a thickness of 0.01~3mm.

[0012] Step 5, using laser to perform surface state control treatment on the ternary composite film prepared above; The appropriate laser power is selected according to the thermal stability of the composite film and the laser treatment effect. The laser energy is not higher than 70% of the film laser damage threshold obtained by the 1-on-1 laser damage test in the ISO 21254-2:2011 standard. The scanning speed is 1~10mm / s. The linear scanning method is adopted, and the laser beam scans from one point to the next point to ensure that the laser beam covers the entire film surface, and finally obtains the ternary composite film treated with high-energy laser irradiation.

[0013] The core friction layer is prepared into a friction nanogenerator according to the following steps: Step 6, performing metal coating on the surface of the ternary composite film prepared in step 5, and then bonding the metal film to the first substrate via the first supporting layer, and leading out the first electrode between the metal film and the first supporting layer to construct a first friction pair of the friction nanogenerator; Step 7: Take the metal-based friction material, bond it to the second substrate through the second supporting layer, and lead out a second electrode between the metal-based friction material and the second supporting layer to construct a second friction pair of the friction nanogenerator; Step 8: Assemble the two friction pairs prepared in step 6 and step 7 into a friction nanogenerator in any one of the modes: horizontal sliding mode, vertical contact-separation mode, single electrode mode, and free vibration mode.

[0014] The natural mineral in step 1 is any one of quartz, bauxite, attapulgite, montmorillonite, corundum, zircon, olivine, crystal, talc, fluorite, diatomaceous earth, calcium silicate, kaolin, mica, feldspar, talc, sillimanite, andalusite, kyanite, and mullite.

[0015] The cleaning solution in step 1 is any one of ethanol, isopropanol, acetone, acetic acid, methanol, ethanol, ammonia water or chloroform, or a mixture of any two of the ethanol, isopropanol, acetone, acetic acid, methanol, ethanol, ammonia water and chloroform in any volume ratio.

[0016] The modifying liquid in step 2 is any one of 3-aminopropyltriethoxysilane, 3-aminopropyltrichlorosilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-vinyltrichlorosilane, 3-vinyltriethoxysilane, γ-vinyltrimethoxysilane, vinyltriethoxysilane, and 3-vinylpropyltriethoxysilane.

[0017] The carbon-based nanomaterial in step 3 is any one of carbon nanotubes, graphene, carbon nanofibers, carbon quantum dots, carbon nanoparticles, multi-walled carbon nanotubes, and single-walled carbon nanotubes.

[0018] The oxidant in step 3 is any one of concentrated nitric acid, potassium permanganate, hydrogen peroxide, sulfuric acid, sodium chlorate, nitrogen oxides, potassium chlorate, chlorine dioxide, perchloric acid, and sodium hypochlorite.

[0019] The protective atmosphere in step 4 may be any one of helium, nitrogen, argon, krypton and neon.

[0020] The thermosetting polymer precursor in step 4 is any one of commercial epoxy resin precursors, polyimide precursors, phenolic resin precursors, unsaturated polyester resin precursors, polyurethane precursors, polysulfide resin precursors, polybenzothiophene precursors, polyesteramide resin precursors, polysiloxane precursors, and polyphenylene ether resin precursors.

[0021] The thermoplastic polymer in step 4 is any one of polydimethylsiloxane, polyetheretherketone, polyphenylene sulfide, polytetrafluoroethylene, polyamide, polysulfone, polycarbonate, polyurethane, and polyarylene.

[0022] The laser in step 5 is any one of continuous laser, nanosecond laser, picosecond laser, and femtosecond laser, and the wavelength covers the extreme ultraviolet to far infrared band.

[0023] The metal film in steps 6 and 7 is any one of a copper film, a titanium film, a gold film, a platinum film, an aluminum film, a nickel film, a silver film, a molybdenum film, a niobium film, and a chromium film.

[0024] The substrate in steps 6 and 7 is any one of polytetrafluoroethylene, polyimide, polyetherimide, polyphenylene sulfide, polyetheretherketone, aramid fiber composite material, polyarylate, glass fiber reinforced epoxy resin, aluminum oxide, zirconium oxide, magnesium oxide, and silicon nitride.

[0025] The support layer in steps 6 and 7 is any one of polyimide, polyetherimide, polytetrafluoroethylene, polyphenylene sulfide, polyamide, polytrimethylene terephthalate, polyarylether, silicone, polysulfone, polyamide-imide, polyaromatic polyester, aluminum-based composite material, aluminum oxide, silicon nitride, silicone rubber, and fluororubber.

[0026] The wires in steps 6 and 7 are any one of copper, titanium, silver, gold, platinum, iron, manganese, aluminum, chromium, nickel or a mixture of the above materials in any proportion and are conductive linear objects, and their surfaces may be covered with one or more layers of insulating materials.

[0027] The metal-based friction material in step 7 is any one of copper foil, titanium foil, gold foil, platinum foil, aluminum foil, nickel foil, and silver foil.

[0028] The present invention first constructs a highly heat-resistant and highly stable polymer / natural mineral / carbon-based nanomaterial ternary composite film substrate, and then uses high-energy laser irradiation treatment to reduce the surface defect density and inhibit the thermal electron generation characteristics under high temperature, thereby obtaining an effective core friction layer material that can withstand extreme environments, ultimately ensuring that the prepared friction nanogenerator can work efficiently, stably and for a long time under extreme conditions over a wide temperature range.

[0029] The beneficial effects of the present invention are as follows: on the one hand, natural minerals and carbon-based nanomaterials with good friction properties and high temperature resistance are added to the high temperature resistant polymer for doping and compounding, so as to prepare a polymer / natural mineral / carbon-based nanomaterial composite film, which enhances the overall high temperature resistance of the friction layer and improves the electrostatic charge; on the other hand, the high energy laser surface state control technology is used to further carry out laser irradiation treatment on the film surface, and by repairing or eliminating the micro defects on the surface, the potential barrier of the friction layer surface to charge binding is increased, and the thermal electron emission effect at high temperature is suppressed, so that the friction layer is more stable at high temperature and has a higher electrostatic charge, thereby improving the power generation efficiency. The friction nanogenerator prepared by using the above friction layer material solves the problem of performance degradation or even complete failure of traditional friction nanogenerators in extreme environments with a wide temperature range, broadens the application field, provides a new solution for energy collection in extreme environments, and achieves the purpose of the present invention.

[0030] In summary, the present invention has the following advantages: 1. Through the combined method of ternary doping composite of the matrix and laser irradiation surface state regulation, the overall mechanical properties and electrical output stability of the core friction layer material under extreme conditions in a wide temperature range are improved.

[0031] 2. The friction nanogenerator prepared based on the present invention can operate stably in extreme environments of -40~200℃ and 0.1~20 standard atmospheric pressures, solving the problem that the previous friction nanogenerator technology can only be used at room temperature.

[0032] 3. The device prepared by the present invention has a simple structure and can be extremely miniaturized. It is particularly suitable for narrow and high-temperature extreme environment spaces that are difficult for conventional electromagnetic generators to enter, such as extremely narrow areas deep underground or under mines. It has very large potential application fields and value.

[0033] 4. The friction nanogenerator prepared based on this core friction layer is a pure solid-state structure, without liquid medium, and will not explode or other dangerous situations under high temperature and high pressure, avoiding the problem of conventional liquid medium chemical batteries such as lithium batteries that are prone to explosion under high temperature and high pressure. DETAILED DESCRIPTION

[0034] In order to clearly illustrate the technical features of this patent, this patent is elaborated in detail below through a specific implementation method.

[0035] Example 1: In this example, quartz is used as the natural mineral, graphene is used as the carbon-based nanomaterial, and epoxy resin is used as the thermosetting polymer.

[0036] The quartz was soaked in ethanol, ultrasonically cleaned for 15 minutes, then rinsed with deionized water, and then placed in an oven and dried at 60°C for 3 hours. The cleaned quartz was soaked in 3-aminopropyltriethoxysilane modified solution, stirred for 30 minutes, and then taken out and dried at 100°C for 2 hours. Then, the graphene was mixed with concentrated nitric acid, reacted at 60°C for 8 hours, washed with deionized water, and dried at 80°C for 4 hours. 2g of modified quartz and 0.5g of graphene treated with concentrated nitric acid were added to 5g of epoxy resin precursor (the mass was measured by the epoxy resin content therein), stirred at high speed for 20 minutes, and then the above solution was poured into a mold with a flat bottom surface. After drying at room temperature for 10 hours, a film was formed; then the film was freeze-dried at a temperature of -40°C and an air pressure of 1Pa, and kept warm for 10 hours; then cured at 220°C for 2 hours under a nitrogen protective atmosphere, and the prepared film thickness was 0.05mm. The surface state of the above film was irradiated and regulated by a 1064nm, 12ns laser. The laser power was 3W, the scanning speed was 5mm / s, and a linear scanning method was used. After scanning at one point, it entered the next point. The spot diameter ensured that the laser beam covered the entire surface of the film, and finally a ternary composite film treated with high-energy laser irradiation was obtained. A copper film with a thickness of 2μm was plated on one side of the above ternary composite film using a conventional vacuum physical deposition method. Then, this copper film was bonded to a polytetrafluoroethylene substrate through a polyimide support layer, and a copper electrode was drawn between the copper film and the support layer to construct a friction pair of a friction nanogenerator. The other friction pair used the same structure as the above friction pair, except that the copper-plated ternary composite film was replaced with nickel foil.

[0037] The two friction pairs were assembled into a horizontal sliding mode triboelectric nanogenerator. Test results showed that the prepared triboelectric nanogenerator had an output voltage of 106.3V and a current of 1.2μA at 180°C and 10 standard atmospheres, and had excellent mechanical and electrical properties.

[0038] Example 2: In this example, bauxite is used as the natural mineral, carbon nanotubes are used as the carbon-based nanomaterials, and polytetrafluoroethylene is used as the thermoplastic polymer.

[0039] Soak the bauxite in acetone, ultrasonically clean it for 10 minutes, then rinse it with deionized water, and then put it in an oven to dry at 120°C for 3.5 hours. Soak the cleaned bauxite in 3-aminopropyltriethoxysilane modification liquid, stir it for 25 minutes, take it out and dry it at 90°C for 2.5 hours. Then, mix the carbon nanotubes with concentrated nitric acid, react at 50°C for 3 hours, wash it with deionized water, and dry it at 75°C for 2 hours. At 340°C, add 1.8g of modified bauxite and 0.2g of oxidized carbon nanotubes to 5.3g of polytetrafluoroethylene and mechanically mix it for 25 minutes; after cooling, put it in a hot press at 340°C, heat it to a molten state, and then keep it at a pressure of 10MPa for 15 minutes; finally, slowly cool it to room temperature to obtain a film with a thickness of 0.06mm. The surface state of the above film was irradiated and regulated by 532 nm, 8ps laser. The laser power was 0.5 W, the scanning speed was 6 mm / s, and the linear scanning method was used. After scanning at one point, it entered the next point. The spot diameter ensured that the laser beam covered the entire surface of the film, and finally a ternary composite film treated with high-energy laser irradiation was obtained. A conventional vacuum physical deposition method was used to plate an aluminum film with a thickness of 0.2μm on one side of the above ternary composite film. Then, this aluminum film was bonded to the polyphenylene sulfide substrate through a polyaryletherimide support layer. A silver electrode was drawn between the aluminum film and the support layer to construct a friction pair of a friction nanogenerator. The other friction pair used the same structure as the above friction pair, except that the aluminum-plated ternary composite film was replaced with silver foil.

[0040] The two friction pairs were assembled into a triboelectric nanogenerator in a vertical contact-separation mode. Test results showed that the prepared triboelectric nanogenerator had an output voltage of 283.8V and a current of 3.1μA at -20°C and 7 standard atmospheric pressures, and had excellent mechanical and electrical properties.

[0041] Example 3: In this example, kyanite is used as the natural mineral, carbon nanotubes are used as the carbon-based nanomaterial, and polyimide is used as the thermosetting polymer.

[0042] Soak the kyanite in isopropanol, ultrasonically clean it for 20 minutes, then rinse it with deionized water, and then put it in an oven to dry at 80°C for 4 hours. Soak the cleaned kyanite in γ-aminopropyltrimethoxysilane modification liquid, stir it for 40 minutes, take it out and dry it at 120°C for 2 hours. Then, mix the carbon nanotubes with hydrogen peroxide, react it at 60°C for 6 hours, wash it with deionized water, and dry it at 80°C for 3 hours. 1.5g of modified kyanite and 0.4g of carbon nanotubes treated with hydrogen peroxide were added to 4.5g of polyimide precursor (the mass was calculated by the polyimide content therein), stirred at high speed for 25min, and then the above solution was poured into a mold with a flat bottom surface, and dried at room temperature for 18h to form a film; then the film was freeze-dried at a temperature of -30°C and an air pressure of 10Pa for 40h; then cured at 300°C for 3h under an argon protective atmosphere, and the prepared film thickness was 0.1mm. Then, a 1064 nm continuous laser was used to regulate the surface state of the above film, with a laser power of 5W and a scanning speed of 7 mm / s. A linear scanning method was used, and after scanning at one point, it entered the next point. The spot diameter ensured that the laser beam covered the entire film surface, and finally a ternary composite film treated with high-energy laser irradiation was obtained. A platinum film with a thickness of 1.5 μm was plated on one side of the above-mentioned ternary composite film by conventional vacuum physical deposition method, and then the platinum film was bonded to the polytetrafluoroethylene substrate through a polyimide support layer, and a silver electrode was drawn between the platinum film and the support layer to construct a friction pair of the friction nanogenerator. The other friction pair has the same structure as the above-mentioned friction pair, except that the platinum-plated ternary composite film is replaced with copper foil.

[0043] The two friction pairs were assembled into a triboelectric nanogenerator in a vertical contact-separation mode. The test results showed that the triboelectric nanogenerator had an output voltage of 82.7V and a current of 0.9μA at 200°C and 20 standard atmospheric pressures, and had excellent mechanical and electrical properties.

[0044] Example 4: In this example, kaolin is used as the natural mineral, graphene is used as the carbon-based nanomaterial, and polydimethylsiloxane is used as the thermoplastic polymer.

[0045] Soak the kaolin in ethanol, ultrasonically clean it for 15 minutes, then rinse it with deionized water, and then put it in an oven to dry at 100°C for 2.5 hours. Then, soak the cleaned kaolin in γ-aminopropyltrimethoxysilane modification liquid, stir it for 30 minutes, take it out and dry it at 130°C for 1 hour. Then, mix the graphene with hydrogen peroxide, react it at 60°C for 5 hours, rinse it with deionized water, and dry it at 90°C for 2 hours. At 380°C, add 1.6g of modified kaolin and 0.4g of oxidized graphene to 4.6g of polydimethylsiloxane and mix it mechanically for 20 minutes; after cooling, put it in a hot press at 190°C, heat it to a molten state, and then keep it at a pressure of 7MPa for 13 minutes; finally, slowly cool it to room temperature to obtain a film with a thickness of 0.3mm. Then, the surface state of the film was irradiated and regulated by 800 nm, 30fs laser. The laser power was 0.1W, the scanning speed was 10mm / s, and the linear scanning method was used. After scanning at one point, it entered the next point. The spot diameter ensured that the laser beam covered the entire surface of the film, and finally a ternary composite film treated with high-energy laser irradiation was obtained. A gold film with a thickness of 0.05μm was plated on one side of the ternary composite film using a conventional vacuum physical deposition method. Then, this gold film was bonded to the polytetrafluoroethylene substrate through a polyphenylene sulfide support layer, and a silver electrode was drawn between the gold film and the support layer to construct a friction pair of a friction nanogenerator. The other friction pair used the same structure as the above friction pair, except that the gold-plated ternary composite film was replaced with nickel foil.

[0046] The two friction pairs were assembled into a horizontal sliding mode triboelectric nanogenerator. The test results showed that the prepared triboelectric nanogenerator had an output voltage of 135.7V and a current of 1.5μA at 100°C and 10 standard atmospheric pressures, and had excellent mechanical and electrical properties.

[0047] Example 5: In this example, mullite is used as the natural mineral, graphene is used as the carbon-based nanomaterial, and phenolic resin is used as the thermosetting polymer.

[0048] Mullite was soaked in isopropanol, ultrasonically cleaned for 20 minutes, then rinsed with deionized water, and then placed in an oven and dried at 80°C for 4 hours. Then, the cleaned mullite was soaked in vinyl triethoxysilane modified solution, stirred for 40 minutes, taken out and dried at 120°C for 2 hours. Then, graphene was mixed with potassium permanganate, reacted at 70°C for 6 hours, washed with deionized water, and dried at 75°C for 5 hours. 1.2g of modified mullite and 0.3g of graphene treated with potassium permanganate were added to 4g of phenolic resin precursor (the mass was calculated by the phenolic resin content therein), stirred at high speed for 28 minutes, and then the above solution was poured into a mold with a flat bottom surface, and a film was formed after drying at room temperature for 18 hours; then the film was freeze-dried at a temperature of -50°C, an air pressure of 0.1Pa, and kept warm for 8 hours; then cured at 250°C for 4 hours under a helium protective atmosphere, and the prepared film thickness was 0.08mm. The surface state of the above-mentioned film was irradiated and regulated by a 1064nm, 1ns laser. The laser power was 3.5W, the scanning speed was 1mm / s, and a linear scanning method was used. After scanning at one point, it entered the next point. The spot diameter ensured that the laser beam covered the entire surface of the film, and finally a ternary composite film treated with high-energy laser irradiation was obtained. A silver film with a thickness of 500μm was plated on one side of the above-mentioned ternary composite film using a conventional vacuum physical deposition method. Then, this layer of silver film was bonded to the polyphenylene sulfide substrate through a polytetrafluoroethylene support layer, and a silver electrode was drawn between the silver film and the support layer to construct a friction pair of a friction nanogenerator. The other friction pair adopted the same structure as the above-mentioned friction pair, except that the silver-plated ternary composite film was replaced with platinum foil.

[0049] The two friction pairs were assembled into a horizontal sliding mode triboelectric nanogenerator. Test results showed that the prepared triboelectric nanogenerator had an output voltage of 210.3V and a current of 2.2μA at -40°C and 0.1 standard atmospheric pressure, and had excellent mechanical and electrical properties.

[0050] There are many specific implementation ways of the present invention. The above is only the preferred implementation mode of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements can be made without departing from the principle of the present invention. These improvements should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing a core friction layer of a friction nanogenerator for use in a wide temperature range extreme environment, characterized in that: The core friction layer is a ternary composite film formed by a composite of polymer, natural mineral and carbon-based nanomaterial and subjected to surface state regulation by high-energy laser irradiation; wherein the mass ratio of high-temperature resistant polymer, natural mineral and carbon-based nanomaterial is 1:0.12~0.50:0.01~0.18; The core friction layer is prepared according to the following steps: Step 1: Take natural minerals, wash and dry them; Soak the natural mineral in the cleaning solution, perform ultrasonic cleaning for 5-20 minutes, then rinse with deionized water, and dry in an oven at 60-150°C for 0.5-5 hours; Step 2, modifying the natural minerals; Soak the cleaned natural minerals in the modified solution, stir for 5-50 minutes, take them out and dry them at 80-150℃ for 0.2-8 hours; Step 3, taking the carbon-based nanomaterial and performing oxidation treatment; First, the carbon-based nanomaterials are mixed with an oxidant, and then reacted at 20-80°C for 1-12 hours, followed by washing with deionized water and finally drying at 60-80°C. Step 4: taking a high temperature resistant polymer, compounding it with the modified natural mineral and the oxidized carbon-based nanomaterial to form a polymer / natural mineral / carbon-based nanomaterial ternary composite film; Wherein, the high temperature resistant polymer is a thermosetting polymer or a thermoplastic polymer; When the high temperature resistant polymer is a thermosetting polymer, the composite method of the thermosetting polymer, the natural mineral and the carbon-based nanomaterial is as follows: adding the modified natural mineral and the oxidized carbon-based nanomaterial to the thermosetting polymer precursor, stirring at high speed for 5 to 60 minutes, then pouring the solution into a mold with a flat bottom, and drying at room temperature for 5 to 20 hours to form a film; then freeze-drying the film at a temperature of -50 to -20°C, an air pressure of 0.1 to 10Pa, and keeping warm for 5 to 40 hours; then curing at 80 to 400°C for 0.5 to 4 hours under a protective atmosphere, and the prepared film has a thickness of 0.01 to 3 mm; When the high temperature resistant polymer is a thermoplastic polymer, the composite method of the thermoplastic polymer, natural minerals and carbon-based nanomaterials is as follows: at a temperature of 220~400°C, the modified natural minerals and the oxidized carbon-based nanomaterials are added to the thermoplastic polymer and mechanically mixed for 10~30 minutes; after cooling, the mixture is placed in a hot press at a temperature of 250~450°C and a pressure of 5~10MPa for 5~15 minutes; finally, a film is obtained after cooling to room temperature with a thickness of 0.01~3mm.

2. Step 5, using laser to perform surface state control treatment on the ternary composite film prepared above; A linear scanning method is used, scanning from one point to the next point, ensuring that the laser beam covers the entire film surface, and finally obtaining a ternary composite film treated with high-energy laser irradiation.

3. The method for preparing a core friction layer of a friction nanogenerator for use in a wide temperature range extreme environment according to claim 1, characterized in that: The natural mineral in step 1 is any one of quartz, bauxite, attapulgite, montmorillonite, corundum, zircon, olivine, crystal, talc, fluorite, diatomaceous earth, calcium silicate, kaolin, mica, feldspar, talc, sillimanite, andalusite, kyanite, and mullite.

4. The method for preparing a core friction layer of a triboelectric nanogenerator for use in a wide temperature range extreme environment according to claim 1, characterized in that: The modifying liquid in step 2 is any one of 3-aminopropyltriethoxysilane, 3-aminopropyltrichlorosilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-vinyltrichlorosilane, 3-vinyltriethoxysilane, γ-vinyltrimethoxysilane, vinyltriethoxysilane, and 3-vinylpropyltriethoxysilane.

5. The method for preparing a core friction layer of a friction nanogenerator for use in a wide temperature range extreme environment according to claim 1, characterized in that: The carbon-based nanomaterial in step 3 is any one of carbon nanotubes, graphene, carbon nanofibers, carbon quantum dots, carbon nanoparticles, multi-walled carbon nanotubes, and single-walled carbon nanotubes.

6. The method for preparing a core friction layer of a friction nanogenerator for use in a wide temperature range extreme environment according to claim 1, characterized in that: The thermosetting polymer precursor in step 4 is any one of commercial epoxy resin precursors, polyimide precursors, phenolic resin precursors, unsaturated polyester resin precursors, polyurethane precursors, polysulfide resin precursors, polybenzothiophene precursors, polyesteramide resin precursors, polysiloxane precursors, and polyphenylene ether resin precursors; The thermoplastic polymer in step 4 is any one of polydimethylsiloxane, polyetheretherketone, polyphenylene sulfide, polytetrafluoroethylene, polyamide, polysulfone, polycarbonate, polyurethane, and polyarylene.

7. A method for applying the core friction layer of a triboelectric nanogenerator prepared according to claim 1 for use in a wide temperature range extreme environment, characterized in that: The core friction layer is prepared into a friction nanogenerator according to the following steps: Step 6, performing metal coating on the surface of the ternary composite film prepared in step 5, and then bonding the metal film to the first substrate via the first supporting layer, and leading out the first electrode between the metal film and the first supporting layer to construct a first friction pair of the friction nanogenerator; Step 7: Take the metal-based friction material, bond it to the second substrate through the second supporting layer, and lead out a second electrode between the metal-based friction material and the second supporting layer to construct a second friction pair of the friction nanogenerator; Step 8: Assemble the two friction pairs prepared in step 6 and step 7 into a friction nanogenerator in any one of the modes: horizontal sliding mode, vertical contact-separation mode, single electrode mode, and free vibration mode.