CN111370565A - Radiation refrigeration thermoelectric film and preparation method thereof - Google Patents
Radiation refrigeration thermoelectric film and preparation method thereof Download PDFInfo
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- 230000005855 radiation Effects 0.000 title claims abstract description 63
- 238000005057 refrigeration Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 25
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- 229920000642 polymer Polymers 0.000 claims description 12
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- SKRWFPLZQAAQSU-UHFFFAOYSA-N stibanylidynetin;hydrate Chemical compound O.[Sn].[Sb] SKRWFPLZQAAQSU-UHFFFAOYSA-N 0.000 claims description 3
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- 239000000463 material Substances 0.000 abstract description 6
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 230000005678 Seebeck effect Effects 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
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- 239000011669 selenium Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/13—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the heat-exchanging means at the junction
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/023—Silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a radiation refrigeration thermoelectric film and a preparation method thereof. The conductive circuit is characterized in that additives comprising bismuth telluride and alloy thereof, silicon powder, silicon dioxide wires, titanium dioxide, indium tin oxide and nano silicon carbide are made into a multilayer-structure insulating film, and a metal conductive circuit is combined. The film can be applied to various outdoor occasions, such as vehicles, aircrafts, various buildings, desert areas and other equipment or buildings. The solar thermal insulation material is arranged on the thermal absorption layer, the radiation refrigeration layer is arranged on the thermal absorption layer, and the radiation refrigeration layer is arranged on the thermal absorption layer. The material has the advantages of cheap and easily-obtained raw materials, simple preparation method, good heat insulation effect, antibacterial and self-cleaning effects, and belongs to a multifunctional environment-friendly material.
Description
Technical Field
The invention relates to the field of thermoelectric functional materials, in particular to a radiation refrigeration thermoelectric film and a preparation method thereof.
Background
At present, a large part of domestic electric energy is converted from heat energy, such as thermal power plants, nuclear power plants and large-scale solar power plants. In these industrial sectors, the conversion between energy is mainly the heating of liquid or steam by means of thermal energy to drive turbines for the generation of electricity. The energy conversion process is complex, the equipment is expensive and is easy to consume, and particularly, the environmental pollution is serious. Different from the traditional thermoelectric conversion method, the thermoelectric conversion device directly performs thermoelectric power generation by utilizing waste heat and waste heat, so that the problem of energy shortage can be effectively relieved, and the reduction of environmental pollution is facilitated.
The thermoelectric semiconductor is a pollution-free green energy product which directly converts heat energy and electric energy by adopting a thermoelectric effect. The thermoelectric power generation utilizes the Seebeck effect of thermoelectric materials to directly convert heat energy into electric energy without mechanical moving parts and chemical reaction. Thermoelectric refrigeration utilizes the peltier effect, and when current flows through a thermoelectric material, heat energy is discharged from a low-temperature end to a high-temperature end, so that a compressor or a refrigerant such as freon is not required. Therefore, the two types of thermoelectric equipment have no vibration, no noise, no abrasion, no leakage, small volume, light weight, safety, reliability and long service life, do not produce any pollution to the environment and are very ideal power supplies and refrigerators. Therefore, related departments of developed countries such as the U.S. department of energy and the japan space and space agency put thermoelectric technology into a medium and long term energy development plan, and China also puts thermoelectric into a new energy plan for large-scale development of a national key basic research and development plan (973). At present, the raw material of the commercial thermoelectric industry is mainly Bi2Te 3-based thermoelectric semiconductor material. The commercialized B i2Te 3-based thermoelectric semiconductor material takes byproducts of bismuth, tellurium, selenium and the like in the copper smelting industry as raw materials, and Bi2Te 3-based thermoelectric semiconductor crystal bars are obtained by oriented growth according to a certain proportion and special doping.
With the increasing shortage of energy supply, how to recycle waste heat has become an important issue, and people are becoming aware of the importance of generating electricity with low grade and waste heat to solve environmental and energy problems. The semiconductor thermoelectric power generation is particularly suitable for recycling low-grade energy. From the technical point of view, the lower the waste heat temperature is, the greater the technical difficulty of utilization is. When power is generated by thermoelectric conversion, the temperature is not limited, and the temperature may be lower than 400K. The temperature difference is only a few tens of degrees of low temperature waste heat, and therefore, the potential for thermoelectric conversion is great. These waste heat include low-temperature waste heat of a factory, waste incineration heat, automobile exhaust gas, natural heat, and the like. With the acceleration of industrialization process, the amount of waste heat is huge, and the reasonable utilization of industrial waste heat is an important aspect for solving energy problems. The existing thermoelectric film has complex process, poor heat insulation effect and low thermoelectric conversion rate, and does not have excellent radiation refrigeration performance.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide the radiation refrigeration thermoelectric film which has the advantages of cheap and easily obtained raw materials, good heat insulation effect and high thermoelectric conversion efficiency.
In order to achieve the above purposes, the invention adopts the technical scheme that: a radiation-cooled thermoelectric film comprising a thermoelectric layer, wherein: the upper end of the thermoelectric layer is provided with a heat absorption layer, the lower end of the thermoelectric layer is provided with a radiation refrigeration layer, and the heat absorption layer is used for absorbing external energy to obtain a high-temperature area and heating the thermoelectric layer; the radiation refrigeration layer is used for obtaining a low-temperature area through radiation refrigeration and cooling the thermoelectric layer; the thermoelectric layer is used for converting the temperature difference into electric energy through a thermoelectric effect and outputting the electric energy through a lead.
Preferably, the raw materials of the heat absorbing layer comprise the following components in parts by weight: 5-20 parts of high-temperature resistant polymer, 0.1-10 parts of dispersant, 0.1-5 parts of assistant, 14-29 parts of solvent and 5-20 parts of heat-absorbing layer modified additive;
the thermoelectric layer comprises the following raw materials in parts by weight: 1-10 parts of high-temperature resistant polymer, 0.1-10 parts of dispersant, 0.1-5 parts of assistant, 1-29 parts of solvent, 35-80 parts of thermal electric layer modification additive and 1-10 parts of metal conductive wire;
the radiation refrigeration layer comprises the following raw materials in parts by weight: 5-20 parts of high-temperature resistant polymer, 0.1-10 parts of dispersant, 0.1-5 parts of assistant, 14-29 parts of solvent and 5-20 parts of radiation refrigeration layer modified additive.
Preferably, the heat absorption layer modification additive comprises silicon powder, carbon powder, mica, glass flakes and silicon oxide filaments, and the mass ratio of the silicon powder, the carbon powder, the mica, the glass flakes and the silicon oxide filaments is 2-4:1-2:0.01-0.5:0.01-0.5: 1-2.
Preferably, the silicon powder, the carbon powder, the mica and the glass flake are granular, the particle diameter is 1-100 μm, more preferably 0.2-5 μm, and the silicon oxide filament is filamentous, and the diameter is 0.1-10 μm, more preferably 0.3-1 μm.
Preferably, the thermoelectric layer modifying additive comprises Bi2Te3 and Bi2Te 3-based solid solution alloy and silica wire, wherein the Bi2Te3 and Bi2Te 3-based solid solution alloy is in the form of porous film, the air pore diameter is 1-100 μm, more preferably 1-10 μm, and the silica wire is in the form of wire, the diameter is preferably 0.1-10 μm, more preferably 0.3-1 μm.
Preferably, the radiation refrigerating layer modification additive comprises nano titanium dioxide, nano indium tin oxide, nano tin antimony oxide, nano silicon dioxide and nano silicon carbide, and the mass ratio of the nano silicon carbide, the nano titanium dioxide, the nano silicon dioxide, the nano indium tin oxide and the nano tin antimony oxide is 0.5-1:1-5:1-2:0.5-1: 0.5-1.
Preferably, the nano titanium dioxide, nano indium tin oxide, nano tin antimony oxide, nano silicon dioxide and nano silicon carbide are one or more of sheet, rod, tubular, spherical and core-shell structures, the particle size is 10-2000nm, and further preferably 300-800 nm.
Preferably, the thickness of the radiation refrigeration thermoelectric film is 1-104 μm, the thickness of the heat absorption layer is 1-100 μm, the thickness of the thermoelectric layer is 103-104 μm, and the thickness of the radiation refrigeration layer is 1-200 μm.
The invention also provides a preparation method of the radiation refrigeration thermoelectric film, which is simple.
In order to achieve the above purposes, the invention adopts the technical scheme that: the preparation method of the radiation refrigeration thermoelectric film comprises the following steps
Preparing a radiation refrigeration layer, dissolving other raw materials of the radiation refrigeration layer in a solvent, mixing, and uniformly grinding; manufacturing a thermoelectric layer, preparing Bi2Te3 and Bi2Te 3-based solid solution alloy by a chemical vapor deposition method, a laser thermal deposition method or a hydrothermal method, uniformly evaporating or magnetron sputtering metal films on two sides of the Bi2Te 3-based solid solution alloy, corroding the metal films by a film coating wet method to obtain an additional conductive metal electrode, and leading out a lead; and (3) preparing a heat absorbing layer, dissolving other raw materials of the heat absorbing layer in a solvent, mixing, and uniformly grinding.
The invention has the beneficial effects that: the upper end and the lower end of the thermoelectric layer are respectively provided with the heat-absorbing layer and the radiation refrigerating layer, the heat-absorbing layer absorbs sunlight irradiation to raise the temperature in the daytime, the radiation refrigerating layer cools the heat-absorbing layer and forms a temperature difference with the radiation refrigerating layer through heat radiation, and then the thermoelectric layer outputs electric energy outwards through a thermoelectric effect.
Detailed Description
Example 1
The radiation refrigeration thermoelectric film comprises a thermoelectric layer, wherein a heat absorption layer is arranged at the upper end of the thermoelectric layer, a radiation refrigeration layer is arranged at the lower end of the thermoelectric layer, and the heat absorption layer is used for absorbing external energy to obtain a high-temperature area and heating the thermoelectric layer; the radiation refrigeration layer is used for obtaining a low-temperature area through radiation refrigeration and cooling the thermoelectric layer; the thermoelectric layer is used for converting the temperature difference into electric energy through a thermoelectric effect and outputting the electric energy through a lead. Both ends are divided and are set up heat-sink shell and radiation refrigeration layer about the thermoelectric layer, and the heat-sink shell produces the absorption intensification to sunlight irradiation daytime, and the radiation refrigeration layer forms the difference in temperature through the outside heat dissipation cooling heat-sink shell of thermal radiation and radiation refrigeration layer, and then realizes that the thermoelectric layer passes through the outside output electric energy of thermoelectric effect, and thermoelectric conversion efficiency is high, and thermal-insulated effectual.
The raw materials of the heat absorbing layer comprise the following components in parts by weight: 5-20 parts of high-temperature resistant polymer, 0.1-10 parts of dispersant, 0.1-5 parts of assistant, 14-29 parts of solvent and 5-20 parts of heat-absorbing layer modified additive. The dispersant is one of polyethylene, polypropylene, polystyrene or polyethylene glycol. The auxiliary agent comprises a defoaming agent, a film auxiliary agent and a thickening agent, wherein the defoaming agent is selected from emulsified silicone oil, a higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether or polydimethylsiloxane, the film auxiliary agent is selected from one or more of acrylic resin, epoxy resin, alkyd resin, amino resin, polyester resin, phenolic resin, polyurethane resin, organic silicon resin and organic fluorine resin, and the thickening agent is selected from hydroxyethyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose or carboxymethyl cellulose. The heat absorption layer modification additive comprises silicon powder, carbon powder, mica, glass flakes and silicon oxide wires, wherein the mass ratio of the silicon powder, the carbon powder, the mica, the glass flakes to the silicon oxide wires is 2-4:1-2:0.01-0.5:0.01-0.5: 1-2. The silicon powder, the carbon powder, the mica and the glass flake are granular, and the particle size is 1-100 mu m. The silicon oxide filaments are filamentous and have the diameter of 0.1-10 mu m.
The thermoelectric layer comprises the following raw materials in parts by weight: 1-10 parts of high-temperature resistant polymer, 0.1-10 parts of dispersant, 0.1-5 parts of assistant, 1-29 parts of solvent, 35-80 parts of thermal electric layer modification additive and 1-10 parts of metal conductive wire. The thermoelectric layer modifying additive comprises Bi2Te3 and Bi2Te 3-based solid solution alloy and silicon oxide wires, wherein the Bi2Te3 and Bi2Te 3-based solid solution alloy is in a porous film shape, the air hole particle size is 1-100 mu m, and the silicon oxide wires are in a wire shape, and the diameter is preferably 0.1-10 mu m.
The radiation refrigeration layer comprises the following raw materials in parts by weight: 5-20 parts of high-temperature resistant polymer, 0.1-10 parts of dispersant, 0.1-5 parts of assistant, 14-29 parts of solvent and 5-20 parts of radiation refrigeration layer modified additive. The radiation refrigerating layer modification additive comprises nano titanium dioxide, nano indium tin oxide, nano tin antimony oxide, nano silicon dioxide and nano silicon carbide, wherein the mass ratio of the nano silicon carbide to the nano titanium dioxide to the nano silicon dioxide to the nano indium tin oxide to the nano tin antimony oxide is 0.5-1:1-5:1-2:0.5-1: 0.5-1. The nano titanium dioxide, nano indium tin oxide, nano antimony tin oxide, nano silicon dioxide and nano silicon carbide are in one or more of sheet, rod, tube, sphere and core-shell structures, and the granularity is 10-2000 nm.
The thickness of the radiation refrigeration thermoelectric film is 1-104 μm, the thickness of the heat absorption layer is 1-100 μm, the thickness of the thermoelectric layer is 103-104 μm, and the thickness of the radiation refrigeration layer is 1-200 μm.
The preparation method of the radiation refrigeration thermoelectric film comprises the following steps
Preparing a radiation refrigeration layer, dissolving other raw materials of the radiation refrigeration layer in a solvent, mixing, and uniformly grinding; manufacturing a thermoelectric layer, preparing Bi2Te3 and Bi2Te 3-based solid solution alloy by a chemical vapor deposition method, a laser thermal deposition method or a hydrothermal method, uniformly evaporating or magnetron sputtering metal films on two sides of the Bi2Te 3-based solid solution alloy, corroding the metal films by a film coating wet method to obtain an additional conductive metal electrode, and leading out a lead; and (3) preparing a heat absorbing layer, dissolving other raw materials of the heat absorbing layer in a solvent, mixing, and uniformly grinding. The raw materials of each layer are cheap and easy to obtain, and the preparation method is simple.
Example 2
The radiation refrigeration thermoelectric film comprises a thermoelectric layer, wherein a heat absorption layer is arranged at the upper end of the thermoelectric layer, a radiation refrigeration layer is arranged at the lower end of the thermoelectric layer, and the heat absorption layer is used for absorbing external energy to obtain a high-temperature area and heating the thermoelectric layer; the radiation refrigeration layer is used for obtaining a low-temperature area through radiation refrigeration and cooling the thermoelectric layer; the thermoelectric layer is used for converting the temperature difference into electric energy through a thermoelectric effect and outputting the electric energy through a lead.
The raw materials of the heat absorbing layer comprise the following components in parts by weight: 5-20 parts of high-temperature resistant polymer, 0.1-10 parts of dispersant, 0.1-5 parts of assistant, 14-29 parts of solvent and 5-20 parts of heat-absorbing layer modified additive. The dispersant is one of polyethylene, polypropylene, polystyrene or polyethylene glycol. The auxiliary agent comprises a defoaming agent, a film auxiliary agent and a thickening agent, the auxiliary agent comprises the defoaming agent, the film auxiliary agent and the thickening agent, the defoaming agent is selected from emulsified silicone oil, a higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether or polydimethylsiloxane, the film auxiliary agent is selected from one or more of acrylic resin, epoxy resin, alkyd resin, amino resin, polyester resin, phenolic resin, polyurethane resin, organic silicon resin and organic fluorine resin, and the thickening agent is selected from hydroxyethyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose or carboxymethyl cellulose. . The heat absorption layer modification additive comprises silicon powder, carbon powder, mica, glass flakes and silicon oxide wires, wherein the mass ratio of the silicon powder, the carbon powder, the mica, the glass flakes to the silicon oxide wires is 2-4:1-2:0.01-0.5:0.01-0.5: 1-2. The silicon powder, the carbon powder, the mica and the glass flake are granular, and the particle size is 0.2-5 mu m. The silicon oxide filaments are filamentous and have the diameter of 0.3-1 mu m.
The thermoelectric layer comprises the following raw materials in parts by weight: 1-10 parts of high-temperature resistant polymer, 0.1-10 parts of dispersant, 0.1-5 parts of assistant, 1-29 parts of solvent, 35-80 parts of thermal electric layer modification additive and 1-10 parts of metal conductive wire. The thermoelectric layer modification additive comprises Bi2Te3 and Bi2Te 3-based solid solution alloy and silicon oxide wires, wherein the Bi2Te3 and Bi2Te 3-based solid solution alloy is in a porous film shape, the air hole particle size is 1-10 mu m, and the silicon oxide wires are in a wire shape, and the diameter is preferably 0.3-1 mu m.
The radiation refrigeration layer comprises the following raw materials in parts by weight: 5-20 parts of high-temperature resistant polymer, 0.1-10 parts of dispersant, 0.1-5 parts of assistant, 14-29 parts of solvent and 5-20 parts of radiation refrigeration layer modified additive. The radiation refrigerating layer modification additive comprises nano titanium dioxide, nano indium tin oxide, nano tin antimony oxide, nano silicon dioxide and nano silicon carbide, wherein the mass ratio of the nano silicon carbide to the nano titanium dioxide to the nano silicon dioxide to the nano indium tin oxide to the nano tin antimony oxide is 0.5-1:1-5:1-2:0.5-1: 0.5-1. The nano titanium dioxide, the nano indium tin oxide, the nano antimony tin oxide, the nano silicon dioxide and the nano silicon carbide are one or more of sheet-shaped, rod-shaped, tubular, spherical and core-shell structures, and the granularity is 300-800 nm.
The thickness of the radiation refrigeration thermoelectric film is 1-104 μm, the thickness of the heat absorption layer is 1-100 μm, the thickness of the thermoelectric layer is 103-104 μm, and the thickness of the radiation refrigeration layer is 1-200 μm.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the present invention is not limited thereto, and any equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (9)
1. A radiation-cooled thermoelectric film comprising a thermoelectric layer, wherein: the upper end of the thermoelectric layer is provided with a heat absorption layer, the lower end of the thermoelectric layer is provided with a radiation refrigeration layer, and the heat absorption layer is used for absorbing external energy to obtain a high-temperature area and heating the thermoelectric layer; the radiation refrigeration layer is used for obtaining a low-temperature area through radiation refrigeration and cooling the thermoelectric layer; the thermoelectric layer is used for converting the temperature difference into electric energy through a thermoelectric effect and outputting the electric energy through a lead.
2. A radiation-cooled thermoelectric film as recited in claim 1, wherein: the raw materials of the heat absorbing layer comprise the following components in parts by weight: 5-20 parts of high-temperature resistant polymer, 0.1-10 parts of dispersant, 0.1-5 parts of assistant, 14-29 parts of solvent and 5-20 parts of heat-absorbing layer modified additive;
the thermoelectric layer comprises the following raw materials in parts by weight: 1-10 parts of high-temperature resistant polymer, 0.1-10 parts of dispersant, 0.1-5 parts of assistant, 1-29 parts of solvent, 35-80 parts of thermal electric layer modification additive and 1-10 parts of metal conductive wire;
the radiation refrigeration layer comprises the following raw materials in parts by weight: 5-20 parts of high-temperature resistant polymer, 0.1-10 parts of dispersant, 0.1-5 parts of assistant, 14-29 parts of solvent and 5-20 parts of radiation refrigeration layer modified additive.
3. A radiation cooled thermoelectric film as recited in claim 2, wherein: the heat absorption layer modification additive comprises silicon powder, carbon powder, mica, glass flakes and silicon oxide wires, wherein the mass ratio of the silicon powder, the carbon powder, the mica, the glass flakes to the silicon oxide wires is 2-4:1-2:0.01-0.5:0.01-0.5: 1-2.
4. A radiation cooled thermoelectric film as recited in claim 3, wherein: the silicon powder, the carbon powder, the mica and the glass flake are granular, the particle size is 1-100 mu m, and the silicon oxide filament is filiform and has the diameter of 0.1-10 mu m.
5. A radiation cooled thermoelectric film as recited in claim 2, wherein: the thermoelectric layer modifying additive comprises Bi2Te3 and Bi2Te 3-based solid solution alloy and silicon oxide wires, wherein the Bi2Te3 and Bi2Te 3-based solid solution alloy is in a porous film shape, the air hole particle size is 1-100 mu m, and the silicon oxide wires are in a wire shape, and the diameter is preferably 0.1-10 mu m.
6. A radiation cooled thermoelectric film as recited in claim 2, wherein: the radiation refrigerating layer modification additive comprises nano titanium dioxide, nano indium tin oxide, nano tin antimony oxide, nano silicon dioxide and nano silicon carbide, wherein the mass ratio of the nano silicon carbide to the nano titanium dioxide to the nano silicon dioxide to the nano indium tin oxide to the nano tin antimony oxide is 0.5-1:1-5:1-2:0.5-1: 0.5-1.
7. A radiation-cooled thermoelectric film as recited in claim 6, wherein: the nano titanium dioxide, nano indium tin oxide, nano antimony tin oxide, nano silicon dioxide and nano silicon carbide are in one or more of sheet, rod, tube, sphere and core-shell structures, and the granularity is 10-2000 nm.
8. A radiation-cooled thermoelectric film as recited in claim 1, wherein: the thickness of the heat absorption layer is 1-104 μm, the thickness of the heat absorption layer is 1-100 μm, the thickness of the thermoelectric layer is 103-104 μm, and the thickness of the radiation refrigeration layer is 1-200 μm.
9. A preparation method of a radiation refrigeration thermoelectric film is characterized by comprising the following steps: comprises the following steps
Preparing a radiation refrigeration layer, dissolving other raw materials of the radiation refrigeration layer in a solvent, mixing, and uniformly grinding; manufacturing a thermoelectric layer, preparing Bi2Te3 and Bi2Te 3-based solid solution alloy by a chemical vapor deposition method, a laser thermal deposition method or a hydrothermal method, uniformly evaporating or magnetron sputtering metal films on two sides of the Bi2Te 3-based solid solution alloy, corroding the metal films by a film coating wet method to obtain an additional conductive metal electrode, and leading out a lead; and (3) preparing a heat absorbing layer, dissolving other raw materials of the heat absorbing layer in a solvent, mixing, and uniformly grinding.
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