WO2021003764A1 - Bifunctional composite power generation material for use in center console cover of automobile, and manufacturing method therefor - Google Patents

Bifunctional composite power generation material for use in center console cover of automobile, and manufacturing method therefor Download PDF

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Publication number
WO2021003764A1
WO2021003764A1 PCT/CN2019/096370 CN2019096370W WO2021003764A1 WO 2021003764 A1 WO2021003764 A1 WO 2021003764A1 CN 2019096370 W CN2019096370 W CN 2019096370W WO 2021003764 A1 WO2021003764 A1 WO 2021003764A1
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Prior art keywords
ito glass
spin
parts
power generation
prepared
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PCT/CN2019/096370
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French (fr)
Chinese (zh)
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张敬敏
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山东光韵智能科技有限公司
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Publication of WO2021003764A1 publication Critical patent/WO2021003764A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R7/00—Stowing or holding appliances inside vehicle primarily intended for personal property smaller than suit-cases, e.g. travelling articles, or maps
    • B60R7/04—Stowing or holding appliances inside vehicle primarily intended for personal property smaller than suit-cases, e.g. travelling articles, or maps in driver or passenger space, e.g. using racks
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/212—TiO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • C03C2217/231—In2O3/SnO2
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/29—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
    • C03C2217/948—Layers comprising indium tin oxide [ITO]
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/116—Deposition methods from solutions or suspensions by spin-coating, centrifugation
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/31—Pre-treatment
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/365—Coating different sides of a glass substrate

Definitions

  • the invention relates to the technical field of vehicle accessories, in particular to a dual-function composite power generation material for an automobile center console cover plate and a manufacturing method thereof.
  • Photoelectric conversion is the process of directly converting solar radiation energy into electrical energy through the photovoltaic effect.
  • the principle of this process is that photons transfer energy to electrons to make them move to form an electric current.
  • Thermoelectric conversion refers to the mutual conversion between thermal energy and electrical energy.
  • Thermoelectric effects include Seebeck effect, Peltier effect, Thomson effect (Thompson) effect.
  • Seebeck effect Peltier effect
  • Thompson Thomson effect
  • the discovery of the thermoelectric conversion effect has aroused great interest in the scientific community, because from a macro perspective, the thermoelectric conversion effect means the direct conversion between heat and electrical energy. How to make this effect into energy conversion and utilization in practical applications.
  • the total conversion efficiency of photoelectric conversion and thermoelectric conversion is not high, and for the small area of the light-receiving surface of the car center console cover plate, pure photoelectric conversion or thermoelectric conversion materials are of little significance.
  • the effect of reducing the temperature in the car is also poor.
  • the photoelectric conversion material can only reduce about 3°C-5°C, and the thermoelectric conversion can only reduce 2°C-3°C.
  • the actual effect is not obvious, but the center console in the car is the car body.
  • the main heat-absorbing area is also the most important factor leading to the high temperature in the car. Therefore, how to solve this technical problem is also a pain point that the existing technology has not overcome.
  • the invention aims to provide a composite power generation material with integrated photoelectric conversion and thermoelectric conversion functions, high total efficiency, good temperature drop in the vehicle, and less change in the structure of the vehicle body.
  • a dual-function composite power generation material for automobile center console cover The composite power generation material is divided into two parts: a light-sensitive power generation material and a thermal power generation material. There are five layers of upper lining layer, upper ITO glass, functional layer, lower ITO glass, and bottom lining layer from top to bottom; the thermal power generation material is specifically 20-25 layers of thermal contact surface and bottom surface of the bottom lining layer. Stacked graphene thermoelectric generator, the cold contact surface of the graphene thermoelectric generator is arranged on the bottom surface of the wiper water tank;
  • the manufacturing method of the photovoltaic power generation material includes the following steps:
  • auxiliary materials prepare enough absolute ethanol, enough ether, enough N,N dimethyl diamide, enough nitrogen, enough chlorobenzene, enough isopropanol, enough zinc powder, enough solute 20% hydrochloric acid aqueous solution, sufficient deionized water, sufficient nitric acid aqueous solution with 10% mass fraction of solute, sufficient concentrated sulfuric acid, sufficient mass fraction of 20% hydrogen peroxide aqueous solution;
  • Step 1 Prepare two curved ITO glass plates prepared in step 1), and apply the zinc powder prepared in step 1) step 2 to the upper surfaces of the two ITO glass plates evenly.
  • Stage 1) The hydrochloric acid aqueous solution prepared in step 2 is slowly dripped on the zinc powder until the zinc powder is completely wetted, and kept for 2min-3min.
  • the hydrochloric acid aqueous solution and the zinc powder are washed with ethanol and deionized water respectively until they are completely cleaned, and two pieces are obtained.
  • step 2 Invert the single-sided etched ITO glass obtained in step 1, and then repeat step 1 to obtain two double-sided etched ITO glasses, namely the upper ITO glass to be used and the lower ITO glass to be used;
  • step 1 3Mix the tetrabutyl titanate and diethanolamine prepared in step 1) step 1 with 150 to 160 parts by weight of ethanol, and stir for 1.5h-2h at a rate of 600rpm/min-800rpm/min to obtain a mixed solution A; Mix 15-17 parts by weight of deionized water and 75-80 parts of ethanol to form an alcohol-water mixed solution, which is mixed liquid B; mix and stir evenly with mixed liquid A and mixed liquid B to obtain mixed liquid C, the mixed liquid C is allowed to stand for 28h-30h in a closed environment, and the mixed liquid C is solized to obtain the sol liquid C;
  • step 2 the upper and lower surfaces of the upper and lower ITO glass to be used and the upper and lower surfaces of the lower ITO glass to be used are all subjected to spin coating processing to obtain spin-coated ITO glass and spin-coated ITO glass;
  • step 5 Put the spin-coated ITO glass and spin-coated ITO glass obtained in step 4 in a resistance furnace, and bake at a temperature of 460°C-480°C for 80min-100min to obtain the etched ITO glass and the etched ITO glass;
  • step 7Mix the sodium nitrate and graphite powder prepared in step 1) in step 1, add concentrated sulfuric acid 20 times the mass of the mixed powder and potassium permanganate prepared in step 1) in an ice bath for 2.5h-3h while stirring, then Let stand for 8-10 days, add dropwise the hydrogen peroxide solution prepared in step 1) in step 2 until the reaction solution no longer generates bubbles, dry the water to obtain solid a, adopt step 1) step 2 preparation Clean the solid a 3 times to 5 times with the nitric acid aqueous solution, then rinse with deionized water to PH 7, and dry again to obtain graphene oxide. Mix the graphene oxide with deionized water and use an ultrasonic cell pulverizer to ultrasonically vibrate. The graphene oxide dispersion with a mass concentration of 1.5 mg/ml is ammoniated with a saturated aqueous ammonia solution to obtain an ammoniated GO solution;
  • the lower surface of the ITO glass obtained in step 5 is etched with the mixed solution. And etch the upper surface of the ITO glass, spin-coating uniformly at a spin-coating rate of 4200rpm/min-4500rpm/min and a spin-coating time of 45s-50s, and then place the etched ITO glass and the etched ITO glass on the spin-coated Completely dry at 65°C-70°C in a vacuum environment; then completely immerse the dried upper ITO glass and lower ITO glass in the mixture E obtained in step 8, keep it for 25min-30min, and then prepare in step 1) step 2 Under the protection of a sufficient amount of nitrogen, complete drying at 65°C-70°C and then cool the furnace to room temperature to obtain the final upper ITO glass and the final lower ITO glass;
  • the present invention Compared with the prior art, the present invention has the following advantages: (1) The present invention integrates the functions of photoelectric conversion and thermoelectric conversion, but it is not a simple physical superposition.
  • the thermoelectric conversion material of the present invention uses graphite that already exists in the prior art.
  • the ene stack integrates the thermoelectric structure, but the upper photoelectric conversion layer has been structurally improved and transparent, and the electrothermal transmission of ammoniated graphene oxide that enhances the photoelectric conversion efficiency of the perovskite material and the overall thermal conductivity of the photoelectric material is added Layer (according to research, graphene oxide that is not ammoniated has relatively poor conductivity, while after ammoniated, the conductivity of graphene is enhanced, which is more suitable for matching with perovskites), which solves the problem of accelerated aging caused by self-generated heat of the functional layer during photovoltaic power generation The problem (transmitting heat to the thermoelectric material part, reducing the overall temperature of the photovoltaic material), while improving the temperature difference and heat transfer efficiency of thermoelectric conversion.
  • the photocatalyst effect of titanium dioxide will consume part of the ultraviolet energy and reduce the temperature rise in the car (this part can reduce 1°C), on the other hand, it can disinfect and sterilize and improve the air quality in the car.
  • the super-hydrophilic surface brought by the titanium dioxide layer is actually a self-cleaning face with lotus effect. , Has a good self-cleaning effect. Therefore, the present invention has the characteristics of integrated photoelectric conversion and thermoelectric conversion functions, high overall efficiency, good temperature drop in the vehicle, and less changes in the structure of the vehicle body.
  • a dual-function composite power generation material for automobile center console cover The composite power generation material is divided into two parts: a light-sensitive power generation material and a thermal power generation material.
  • the light-sensitive power generation material is provided with an upper lining layer and an upper lining from top to bottom.
  • the thermal power generation material is specifically a graphene thermoelectric generator with 20-25 layers stacked on the thermal contact surface and the lower surface of the backing layer. The graphene The cold contact surface of the thermoelectric generator is set on the bottom surface of the wiper tank;
  • the manufacturing method of the photovoltaic power generation material includes the following steps:
  • auxiliary materials prepare enough absolute ethanol, enough ether, enough N,N dimethyl diamide, enough nitrogen, enough chlorobenzene, enough isopropanol, enough zinc powder, enough solute 20% hydrochloric acid aqueous solution, sufficient deionized water, sufficient nitric acid aqueous solution with 10% mass fraction of solute, sufficient concentrated sulfuric acid, sufficient mass fraction of 20% hydrogen peroxide aqueous solution;
  • Step 1 Prepare two curved ITO glass plates prepared in step 1), and apply the zinc powder prepared in step 1) step 2 to the upper surfaces of the two ITO glass plates evenly.
  • Stage 1) The hydrochloric acid aqueous solution prepared in step 2 is slowly dripped on the zinc powder until the zinc powder is completely wetted, and kept for 2min-3min.
  • the hydrochloric acid aqueous solution and the zinc powder are washed with ethanol and deionized water respectively until they are completely cleaned to obtain two pieces Etching ITO glass on one side;
  • step 2 Invert the single-sided etched ITO glass obtained in step 1, and then repeat step 1 to obtain two double-sided etched ITO glass, namely the upper ITO glass to be used and the lower ITO glass to be used;
  • step 1 3Mix the tetrabutyl titanate and diethanolamine prepared in step 1) step 1 with 150 to 160 parts by weight of ethanol, and stir for 1.5h-2h at a rate of 600rpm/min-800rpm/min to obtain a mixed solution A; Mix 15-17 parts by weight of deionized water and 75-80 parts of ethanol to form an alcohol-water mixed solution, which is mixed liquid B; mix and stir evenly with mixed liquid A and mixed liquid B to obtain mixed liquid C, the mixed liquid C is allowed to stand for 28h-30h in a closed environment, and the mixed liquid C is solized to obtain the sol liquid C;
  • step 2 the upper and lower surfaces of the upper and lower ITO glass to be used and the upper and lower surfaces of the lower ITO glass to be used are all subjected to spin coating processing to obtain spin-coated ITO glass and spin-coated ITO glass;
  • step 5 Put the spin-coated ITO glass and the spin-coated ITO glass obtained in step 4 in a resistance furnace, and bake at a temperature of 460°C-480°C for 80min-100min to obtain etched ITO glass and etched ITO glass;
  • step 7Mix the sodium nitrate and graphite powder prepared in step 1) in step 1, add concentrated sulfuric acid 20 times the mass of the mixed powder and potassium permanganate prepared in step 1) in an ice bath for 2.5h-3h while stirring, then Let stand for 8-10 days, add dropwise the hydrogen peroxide solution prepared in step 1) in step 2 until the reaction solution no longer generates bubbles, dry the water to obtain solid a, adopt step 1) step 2 preparation Clean the solid a 3 times to 5 times with the nitric acid aqueous solution, then rinse with deionized water to PH 7, and dry again to obtain graphene oxide. Mix the graphene oxide with deionized water and use an ultrasonic cell pulverizer to ultrasonically vibrate. The graphene oxide dispersion with a mass concentration of 1.5 mg/ml is ammoniated with a saturated aqueous ammonia solution to obtain an ammoniated GO solution;
  • the lower surface of the ITO glass obtained in step 5 is etched with the mixed solution. And etch the upper surface of the ITO glass, spin-coating uniformly at a spin-coating rate of 4200rpm/min-4500rpm/min and a spin-coating time of 45s-50s, and then place the etched ITO glass and the etched ITO glass on the spin-coated Completely dry at 65°C-70°C in a vacuum environment; then completely immerse the dried upper ITO glass and lower ITO glass in the mixture E obtained in step 8, keep it for 25min-30min, and then prepare in step 1) step 2 Under the protection of a sufficient amount of nitrogen, complete drying at 65°C-70°C and then cool the furnace to room temperature to obtain the final upper ITO glass and the final lower ITO glass;
  • the overall light/thermoelectric energy conversion rate of the present invention is 26.0%-28.2%, which can turn harm into profit, reduce the temperature in the car by 5°C-8°C on average, and has a self-cleaning function, the same below.
  • the manufacturing method of the photovoltaic power generation material includes the following steps:
  • the manufacturing method of the photovoltaic power generation material includes the following steps:
  • the invention has the characteristics of integrated photoelectric conversion and thermoelectric conversion functions, high total efficiency, good temperature drop in the vehicle, and little change in the structure of the vehicle body.

Abstract

A bifunctional composite power generation material for use in a center console cover of an automobile, and a manufacturing method therefor. The composite power generation material is divided into a photoelectric material and a thermoelectric material. The photoelectric material comprises, from top to bottom, an upper lining layer, upper ITO glass, a functional layer, lower ITO glass, and a bottom lining layer. The thermoelectric material is specifically a graphene thermoelectric generator having 20 to 25 stacked layers. The graphene thermoelectric generator has a thermal contact surface attached to a bottom surface of the bottom lining layer, and has a cold contact surface disposed at a bottom surface of a windshield-wiper water tank. The composite power generation material integrates photoelectric conversion and thermoelectric conversion functions, achieves high overall efficiency, facilitates temperature drops in the vehicle, and does not require many changes made to the vehicle structure.

Description

一种汽车中控台盖板用双功能复合发电材料及其制造方法Dual-function composite power generation material for automobile center console cover plate and manufacturing method thereof 技术领域Technical field
本发明涉及车用配件技术领域，尤其涉及一种汽车中控台盖板用双功能复合发电材料及其制造方法。The invention relates to the technical field of vehicle accessories, in particular to a dual-function composite power generation material for an automobile center console cover plate and a manufacturing method thereof.
背景技术Background technique
光电转换是通过光伏效应把太阳辐射能直接转换成电能的过程。这一过程的原理是光子将能量传递给电子使其运动从而形成电流。这一过程有两种解决途径，最常见的一种是使用以硅为主要材料的固体装置，另一种则是使用光敏染料分子来捕获光子的能量。染料分子吸收光子能量后将使半导体中的带负电的电子和带正电的空穴分离。Photoelectric conversion is the process of directly converting solar radiation energy into electrical energy through the photovoltaic effect. The principle of this process is that photons transfer energy to electrons to make them move to form an electric current. There are two ways to solve this process. The most common one is to use a solid device with silicon as the main material, and the other is to use photosensitive dye molecules to capture the energy of photons. After the dye molecule absorbs the photon energy, it separates the negatively charged electrons from the positively charged holes in the semiconductor.
技术问题technical problem
热电转换是指热能和电能之间的相互转换。热电效应包括塞贝克 (Seebeck) 效应、珀尔帖 (Peltier) 效应、汤姆逊 (Thompson) 效应。热电转换效应的发现，引起了科学界极大的兴趣，因为从宏观上讲，热电转换效应意味着热能与电能之间的直接转换。如何使这种效应成为实际应用中的能量转换与利用。Thermoelectric conversion refers to the mutual conversion between thermal energy and electrical energy. Thermoelectric effects include Seebeck effect, Peltier effect, Thomson effect (Thompson) effect. The discovery of the thermoelectric conversion effect has aroused great interest in the scientific community, because from a macro perspective, the thermoelectric conversion effect means the direct conversion between heat and electrical energy. How to make this effect into energy conversion and utilization in practical applications.
技术解决方案Technical solutions
现有技术中，光电转换与热电转化的总转换效率均不高，而对于汽车中控台盖板这种小区域面积受光受热面而言，单纯的光电转换或热电转换材料均意义不大，同时各自降低车内温度的效果也较差，光电转换材料大约仅能降低3℃-5℃，热电转换仅能降低2℃-3℃，实际效果不显，但车内中控台是车体主要吸热区域，也是导致车内高温最主要的因素，因此如何解决这个技术问题也是现有技术没有攻克的痛点。In the prior art, the total conversion efficiency of photoelectric conversion and thermoelectric conversion is not high, and for the small area of the light-receiving surface of the car center console cover plate, pure photoelectric conversion or thermoelectric conversion materials are of little significance. At the same time, the effect of reducing the temperature in the car is also poor. The photoelectric conversion material can only reduce about 3℃-5℃, and the thermoelectric conversion can only reduce 2℃-3℃. The actual effect is not obvious, but the center console in the car is the car body. The main heat-absorbing area is also the most important factor leading to the high temperature in the car. Therefore, how to solve this technical problem is also a pain point that the existing technology has not overcome.
因此，市面上急需一种集成光电转换与热电转换功能、总效率高、车内温降好、车体结构变动少的复合发电材料。Therefore, there is an urgent need for a composite power generation material that integrates photoelectric conversion and thermoelectric conversion functions, has high overall efficiency, good temperature drop in the car, and less changes in car body structure.
有益效果Beneficial effect
本发明旨在提供一种集成光电转换与热电转换功能、总效率高、车内温降好、车体结构变动少的复合发电材料。The invention aims to provide a composite power generation material with integrated photoelectric conversion and thermoelectric conversion functions, high total efficiency, good temperature drop in the vehicle, and less change in the structure of the vehicle body.
实现上述目的，本发明采用以下技术方案：一种汽车中控台盖板用双功能复合发电材料，该复合发电材料分为光感发电材料和热感发电材料两个部分，其中光感发电材料由上至下设置有上衬层、上ITO玻璃、功能层、下ITO玻璃、底衬层共五层；热感发电材料具体为热触面与底衬层下表面贴合的20-25层堆栈的石墨烯热电发生器，该石墨烯热电发生器的冷触面设置在雨刷水箱的底面；To achieve the above objective, the present invention adopts the following technical solutions: a dual-function composite power generation material for automobile center console cover. The composite power generation material is divided into two parts: a light-sensitive power generation material and a thermal power generation material. There are five layers of upper lining layer, upper ITO glass, functional layer, lower ITO glass, and bottom lining layer from top to bottom; the thermal power generation material is specifically 20-25 layers of thermal contact surface and bottom surface of the bottom lining layer. Stacked graphene thermoelectric generator, the cold contact surface of the graphene thermoelectric generator is arranged on the bottom surface of the wiper water tank;
其中，光感发电材料的制造方法包括以下步骤：Among them, the manufacturing method of the photovoltaic power generation material includes the following steps:
1）原材料准备1) Preparation of raw materials
①原材料准备：按重量份准备钛酸四丁酯50份-55份、二乙醇胺12份-15份、溶质质量分数1.5%的PEDOT：PSS水溶液65份-70份、[6，6]－苯基－C61－丁酸异甲酯16份-18份、高锰酸钾45份-48份、二甲基亚砜50份-55份、足量弧形ITO玻璃板、硝酸钠7份-9份、石墨粉10份-12份、CH3NH3PbI3 12份-15份、足量氨水饱和溶液；①Preparation of raw materials: prepare 50-55 parts of tetrabutyl titanate, 12-15 parts of diethanolamine, 1.5% solute mass fraction of PEDOT: PSS aqueous solution 65-70 parts, [6,6]-benzene by weight Base-C61-isomethyl butyrate 16-18 parts, potassium permanganate 45-48 parts, dimethyl sulfoxide 50-55 parts, sufficient curved ITO glass plate, sodium nitrate 7-9 parts Parts, 10 parts to 12 parts of graphite powder, 12 parts to 15 parts of CH3NH3PbI3, enough saturated ammonia solution;
②辅材准备：准备足量无水乙醇、足量乙醚、足量N,N二甲基二酰胺、足量氮气、足量氯苯、足量异丙醇、足量锌粉、足量溶质质量分数20%的盐酸水溶液、足量去离子水、足量溶质质量分数10%的硝酸水溶液、足量浓硫酸、足量质量分数20%过氧化氢水溶液；② Preparation of auxiliary materials: prepare enough absolute ethanol, enough ether, enough N,N dimethyl diamide, enough nitrogen, enough chlorobenzene, enough isopropanol, enough zinc powder, enough solute 20% hydrochloric acid aqueous solution, sufficient deionized water, sufficient nitric acid aqueous solution with 10% mass fraction of solute, sufficient concentrated sulfuric acid, sufficient mass fraction of 20% hydrogen peroxide aqueous solution;
2）受光区制造方法2) Manufacturing method of light receiving area
①准备两块阶段1）步骤①准备的弧形ITO玻璃板，将阶段1）步骤②准备的锌粉分别均匀涂抹在两块ITO玻璃板的上表面上，涂抹至目视完全覆盖，然后将阶段1）步骤②准备的盐酸水溶液缓慢滴加在锌粉上直至锌粉完全润湿，保持2min-3min，将盐酸水溶液和锌粉采用乙醇和去离子水分别清洗至完全清洗干净，获得两块单面润蚀ITO玻璃；①Prepare two curved ITO glass plates prepared in step 1), and apply the zinc powder prepared in step 1) step ② to the upper surfaces of the two ITO glass plates evenly. Stage 1) The hydrochloric acid aqueous solution prepared in step ② is slowly dripped on the zinc powder until the zinc powder is completely wetted, and kept for 2min-3min. The hydrochloric acid aqueous solution and the zinc powder are washed with ethanol and deionized water respectively until they are completely cleaned, and two pieces are obtained. Etching ITO glass on one side;
②将步骤①获得的单面润蚀ITO玻璃翻转，然后重复一次步骤①，获得两块双面润蚀ITO玻璃，即为待用上ITO玻璃和待用下ITO玻璃；②Invert the single-sided etched ITO glass obtained in step ①, and then repeat step ① to obtain two double-sided etched ITO glasses, namely the upper ITO glass to be used and the lower ITO glass to be used;
③将阶段1）步骤①准备的钛酸四丁酯、二乙醇胺与按重量份计的150份-160份乙醇混合均匀，以600rpm/min-800rpm/min的速率搅拌1.5h-2h，获得混液A；将按重量份计的15份-17份去离子水与75份-80份乙醇混配成醇水混溶液，即为混液B；将混液A和混液B混合并搅拌均匀后，获得混液C，将混液C在密闭环境内静置28h-30h，混液C溶胶化，获得溶胶液C；③Mix the tetrabutyl titanate and diethanolamine prepared in step 1) step ① with 150 to 160 parts by weight of ethanol, and stir for 1.5h-2h at a rate of 600rpm/min-800rpm/min to obtain a mixed solution A; Mix 15-17 parts by weight of deionized water and 75-80 parts of ethanol to form an alcohol-water mixed solution, which is mixed liquid B; mix and stir evenly with mixed liquid A and mixed liquid B to obtain mixed liquid C, the mixed liquid C is allowed to stand for 28h-30h in a closed environment, and the mixed liquid C is solized to obtain the sol liquid C;
④将步骤③获得的溶胶液C以1200rpm/min-1300rpm/min的旋涂速率，每次45s-50s的旋涂时间，旋涂两次，涂层干结后厚度150nm-180nm的工艺，分别在步骤②获得的待用上ITO玻璃的上下两个表面及待用下ITO玻璃的上下表面全部进行旋涂处理，获得旋涂上ITO玻璃和旋涂下ITO玻璃；④Spin the sol solution C obtained in step ③ at a spin-coating speed of 1200rpm/min-1300rpm/min, each spin-coating time of 45s-50s, spin coating twice, the thickness of the coating after drying is 150nm-180nm, respectively In step ②, the upper and lower surfaces of the upper and lower ITO glass to be used and the upper and lower surfaces of the lower ITO glass to be used are all subjected to spin coating processing to obtain spin-coated ITO glass and spin-coated ITO glass;
⑤将步骤④获得的旋涂上ITO玻璃和旋涂下ITO玻璃置于电阻炉中，采用460℃-480℃的温度烘烤80min-100min，获得蚀刻上ITO玻璃和蚀刻下ITO玻璃；⑤ Put the spin-coated ITO glass and spin-coated ITO glass obtained in step ④ in a resistance furnace, and bake at a temperature of 460℃-480℃ for 80min-100min to obtain the etched ITO glass and the etched ITO glass;
⑥将阶段1）步骤①准备的[6，6]－苯基－C61－丁酸异甲酯与阶段1）步骤②准备的氯苯均匀混配成质量浓度20mg/ml的混液D；⑥The [6,6]-phenyl-C61-isomethyl butyrate prepared in step 1) and the chlorobenzene prepared in step ② of step 1) are uniformly mixed into a mixture D with a mass concentration of 20 mg/ml;
⑦将阶段1）步骤①准备的硝酸钠、石墨粉混合均匀，加入混合粉末质量20倍的浓硫酸及阶段1）步骤①准备的高锰酸钾，边搅拌边冰浴2.5h-3h，然后静置8天-10天，在反应液内滴加阶段1）步骤②准备的过氧化氢水溶液至反应液不再产生气泡后，烘干水份，获得固体a，采用阶段1）步骤②准备的硝酸水溶液清洗固体a3次-5次，然后采用去离子水漂洗至PH=7，再次干燥，获得氧化石墨烯，将氧化石墨烯与去离子水混合并采用超声波细胞粉碎机超声震荡混配成质量浓度1.5mg/ml的氧化石墨烯分散液，采用氨水饱和溶液氨化处理氧化石墨烯分散液，获得氨化GO溶液；⑦Mix the sodium nitrate and graphite powder prepared in step 1) in step ①, add concentrated sulfuric acid 20 times the mass of the mixed powder and potassium permanganate prepared in step 1) in an ice bath for 2.5h-3h while stirring, then Let stand for 8-10 days, add dropwise the hydrogen peroxide solution prepared in step 1) in step ② until the reaction solution no longer generates bubbles, dry the water to obtain solid a, adopt step 1) step ② preparation Clean the solid a 3 times to 5 times with the nitric acid aqueous solution, then rinse with deionized water to PH=7, and dry again to obtain graphene oxide. Mix the graphene oxide with deionized water and use an ultrasonic cell pulverizer to ultrasonically vibrate. The graphene oxide dispersion with a mass concentration of 1.5 mg/ml is ammoniated with a saturated aqueous ammonia solution to obtain an ammoniated GO solution;
⑧将阶段1）步骤①准备的CH3NH3PbI3与阶段1）步骤②准备的异丙醇混配成固含物浓度9mg/ml-12mg/ml的混液E；⑧Mix the CH3NH3PbI3 prepared in step 1) step ① and isopropanol prepared in step 1) step ② into a mixture E with a solid content concentration of 9mg/ml-12mg/ml;
⑨将步骤⑥获得的混液D与步骤⑦获得的氨化GO溶液按体积比1：（5-6）混合调配均匀后，将调配后的混合液在步骤⑤获得的蚀刻上ITO玻璃的下表面和蚀刻下ITO玻璃的上表面，以4200rpm/min-4500rpm/min的旋涂速率，45s-50s的旋涂时间均匀旋涂，然后将旋涂后的蚀刻上ITO玻璃和蚀刻下ITO玻璃置于真空环境内采用65℃-70℃完全烘干；再然后将烘干的上ITO玻璃和下ITO玻璃完全浸入步骤⑧获得的混液E中，保持25min-30min，然后在阶段1）步骤②准备的足量氮气保护下，采用65℃-70℃完全烘干然后炉冷至室温，获得终制上ITO玻璃和终制下ITO玻璃；⑨Mix the mixed solution D obtained in step ⑥ with the ammoniated GO solution obtained in step ⑦ according to the volume ratio of 1: (5-6). After the mixed solution is uniformly mixed, the lower surface of the ITO glass obtained in step ⑤ is etched with the mixed solution. And etch the upper surface of the ITO glass, spin-coating uniformly at a spin-coating rate of 4200rpm/min-4500rpm/min and a spin-coating time of 45s-50s, and then place the etched ITO glass and the etched ITO glass on the spin-coated Completely dry at 65℃-70℃ in a vacuum environment; then completely immerse the dried upper ITO glass and lower ITO glass in the mixture E obtained in step ⑧, keep it for 25min-30min, and then prepare in step 1) step ② Under the protection of a sufficient amount of nitrogen, complete drying at 65°C-70°C and then cool the furnace to room temperature to obtain the final upper ITO glass and the final lower ITO glass;
⑩将阶段1）步骤①准备的PEDOT：PSS水溶液以750rpm/min-800rpm/min的旋涂速率、32s-35s的旋涂时间分别旋涂在步骤⑨获得的终制上ITO玻璃的下表面和终制下ITO玻璃的上表面，然后将旋涂好的终制上ITO玻璃的下表面和终制下ITO玻璃的上表面在真空环境内紧密贴合，并在足量氮气保护下烘干35min-40min，随炉冷至室温后取出，获得的复合结构即为所需光感发电材料。⑩Spin-coat the PEDOT:PSS aqueous solution prepared in step 1) step ① at a spin-coating rate of 750rpm/min-800rpm/min and a spin-coating time of 32s-35s on the bottom surface and the final upper ITO glass obtained in step ⑨ Finish the upper surface of the ITO glass, and then the spin-coated lower surface of the final ITO glass and the upper surface of the final ITO glass are tightly attached in a vacuum environment, and dried under the protection of sufficient nitrogen for 35 minutes -40min, take it out after the furnace is cooled to room temperature, the obtained composite structure is the required photovoltaic power generation material.
与现有技术相比较，本发明具有以下优点：（1）本发明集成了光电转换与热电转换功能，但不是简单的物理叠加，本发明的热电转换材料采用了现有技术中已存在的石墨烯堆栈集成热电结构，但对处于上方的光电转换层则进行了结构改进和透明化处理，又增加了增强钙钛矿材料光电转换效率和整体光电材料热导率的氨化氧化石墨烯电热传输层（根据研究，不氨化的氧化石墨烯导电性相对较差，而氨化后石墨烯导电性增强，更适于与钙钛矿匹配），解决了光伏发电时功能层自生热导致加速老化的问题（将热量传输到热电材料部分，减少了光伏材料整体温度），同时提升热电转换的温差和传热效率。（2）降低了车内温度，无论哪个季节（哪怕是冬季），阳光充足的条件下，户外停车时车内温度都会高于外界10℃-20℃，车内闷热不仅会影响人的体感舒适，而且过高的车内温度易导致车内塑料、人造革等相关材料加速老化甚至部分变性分解释放有毒有害物质，本发明通过转换部分光能和热能实现明显降低车内外温差（实测约降低5℃-8℃的温差）的技术效果。（3）ITO玻璃本身就是光滑硬质材料，易主动清洁，表面润蚀后固化了二氧化钛凝胶膜，二氧化钛的光触媒作用一方面会消耗部分紫外线的能量，降低车内温升（这部分能降低1℃左右），另一方面能消毒除菌，改善车内空气质量，最主要的是，用于本发明时，表层的二氧化钛层带来的超亲水表面实际上是具有莲花效应的自洁面，有良好的自洁效果。因而本发明具有集成光电转换与热电转换功能、总效率高、车内温降好、车体结构变动少的特性。Compared with the prior art, the present invention has the following advantages: (1) The present invention integrates the functions of photoelectric conversion and thermoelectric conversion, but it is not a simple physical superposition. The thermoelectric conversion material of the present invention uses graphite that already exists in the prior art. The ene stack integrates the thermoelectric structure, but the upper photoelectric conversion layer has been structurally improved and transparent, and the electrothermal transmission of ammoniated graphene oxide that enhances the photoelectric conversion efficiency of the perovskite material and the overall thermal conductivity of the photoelectric material is added Layer (according to research, graphene oxide that is not ammoniated has relatively poor conductivity, while after ammoniated, the conductivity of graphene is enhanced, which is more suitable for matching with perovskites), which solves the problem of accelerated aging caused by self-generated heat of the functional layer during photovoltaic power generation The problem (transmitting heat to the thermoelectric material part, reducing the overall temperature of the photovoltaic material), while improving the temperature difference and heat transfer efficiency of thermoelectric conversion. (2) The temperature inside the car is lowered. No matter what season (even in winter), under sunny conditions, the temperature inside the car will be 10℃-20℃ higher than the outside when parking outdoors. The sultry inside the car will not only affect people's physical comfort In addition, the excessively high temperature in the car can easily lead to accelerated aging and partial denaturation and decomposition of related materials such as plastic and artificial leather in the car to release toxic and harmful substances. -8℃ temperature difference) technical effect. (3) ITO glass itself is a smooth and hard material, which is easy to clean actively. After the surface is etched, the titanium dioxide gel film is cured. On the one hand, the photocatalyst effect of titanium dioxide will consume part of the ultraviolet energy and reduce the temperature rise in the car (this part can reduce 1℃), on the other hand, it can disinfect and sterilize and improve the air quality in the car. The most important thing is that when used in the present invention, the super-hydrophilic surface brought by the titanium dioxide layer is actually a self-cleaning face with lotus effect. , Has a good self-cleaning effect. Therefore, the present invention has the characteristics of integrated photoelectric conversion and thermoelectric conversion functions, high overall efficiency, good temperature drop in the vehicle, and less changes in the structure of the vehicle body.
本发明的最佳实施方式The best mode of the invention
实施例1：Example 1:
　一种汽车中控台盖板用双功能复合发电材料，该复合发电材料分为光感发电材料和热感发电材料两个部分，其中光感发电材料由上至下设置有上衬层、上ITO玻璃、功能层、下ITO玻璃、底衬层共五层；热感发电材料具体为热触面与底衬层下表面贴合的20-25层堆栈的石墨烯热电发生器，该石墨烯热电发生器的冷触面设置在雨刷水箱的底面；A dual-function composite power generation material for automobile center console cover. The composite power generation material is divided into two parts: a light-sensitive power generation material and a thermal power generation material. The light-sensitive power generation material is provided with an upper lining layer and an upper lining from top to bottom. There are five layers of ITO glass, functional layer, lower ITO glass, and backing layer; the thermal power generation material is specifically a graphene thermoelectric generator with 20-25 layers stacked on the thermal contact surface and the lower surface of the backing layer. The graphene The cold contact surface of the thermoelectric generator is set on the bottom surface of the wiper tank;
　其中，光感发电材料的制造方法包括以下步骤：　Among them, the manufacturing method of the photovoltaic power generation material includes the following steps:
　1）原材料准备　1) Preparation of raw materials
　①原材料准备：按重量份准备钛酸四丁酯52.2Kg、二乙醇胺14.1Kg、溶质质量分数1.5%的PEDOT：PSS水溶液67.4Kg、[6，6]－苯基－C61－丁酸异甲酯17.0Kg、高锰酸钾47.4Kg、足量弧形ITO玻璃板、硝酸钠7.7Kg、石墨粉10.9Kg、CH3NH3PbI3 12.7Kg、足量氨水饱和溶液；①Preparation of raw materials: prepare 52.2Kg of tetrabutyl titanate, 14.1Kg of diethanolamine, 1.5% solute mass fraction of PEDOT: PSS aqueous solution 67.4Kg, [6,6]-phenyl-C61-isomethyl butyrate in parts by weight 17.0Kg, potassium permanganate 47.4Kg, sufficient curved ITO glass plate, sodium nitrate 7.7Kg, graphite powder 10.9Kg, CH3NH3PbI3 12.7Kg, sufficient ammonia water saturated solution;
　②辅材准备：准备足量无水乙醇、足量乙醚、足量N,N二甲基二酰胺、足量氮气、足量氯苯、足量异丙醇、足量锌粉、足量溶质质量分数20%的盐酸水溶液、足量去离子水、足量溶质质量分数10%的硝酸水溶液、足量浓硫酸、足量质量分数20%过氧化氢水溶液；② Preparation of auxiliary materials: prepare enough absolute ethanol, enough ether, enough N,N dimethyl diamide, enough nitrogen, enough chlorobenzene, enough isopropanol, enough zinc powder, enough solute 20% hydrochloric acid aqueous solution, sufficient deionized water, sufficient nitric acid aqueous solution with 10% mass fraction of solute, sufficient concentrated sulfuric acid, sufficient mass fraction of 20% hydrogen peroxide aqueous solution;
　2）受光区制造方法　2) Manufacturing method of light receiving area
　①准备两块阶段1）步骤①准备的弧形ITO玻璃板，将阶段1）步骤②准备的锌粉分别均匀涂抹在两块ITO玻璃板的上表面上，涂抹至目视完全覆盖，然后将阶段1）步骤②准备的盐酸水溶液缓慢滴加在锌粉上直至锌粉完全润湿，保持2min-3min，将盐酸水溶液和锌粉采用乙醇和去离子水分别清洗至完全清洗干净，获得两块单面润蚀ITO玻璃；①Prepare two curved ITO glass plates prepared in step 1), and apply the zinc powder prepared in step 1) step ② to the upper surfaces of the two ITO glass plates evenly. Stage 1) The hydrochloric acid aqueous solution prepared in step ② is slowly dripped on the zinc powder until the zinc powder is completely wetted, and kept for 2min-3min. The hydrochloric acid aqueous solution and the zinc powder are washed with ethanol and deionized water respectively until they are completely cleaned to obtain two pieces Etching ITO glass on one side;
　②将步骤①获得的单面润蚀ITO玻璃翻转，然后重复一次步骤①，获得两块双面润蚀ITO玻璃，即为待用上ITO玻璃和待用下ITO玻璃；　②Invert the single-sided etched ITO glass obtained in step ①, and then repeat step ① to obtain two double-sided etched ITO glass, namely the upper ITO glass to be used and the lower ITO glass to be used;
　③将阶段1）步骤①准备的钛酸四丁酯、二乙醇胺与按重量份计的150份-160份乙醇混合均匀，以600rpm/min-800rpm/min的速率搅拌1.5h-2h，获得混液A；将按重量份计的15份-17份去离子水与75份-80份乙醇混配成醇水混溶液，即为混液B；将混液A和混液B混合并搅拌均匀后，获得混液C，将混液C在密闭环境内静置28h-30h，混液C溶胶化，获得溶胶液C；③Mix the tetrabutyl titanate and diethanolamine prepared in step 1) step ① with 150 to 160 parts by weight of ethanol, and stir for 1.5h-2h at a rate of 600rpm/min-800rpm/min to obtain a mixed solution A; Mix 15-17 parts by weight of deionized water and 75-80 parts of ethanol to form an alcohol-water mixed solution, which is mixed liquid B; mix and stir evenly with mixed liquid A and mixed liquid B to obtain mixed liquid C, the mixed liquid C is allowed to stand for 28h-30h in a closed environment, and the mixed liquid C is solized to obtain the sol liquid C;
　④将步骤③获得的溶胶液C以1200rpm/min-1300rpm/min的旋涂速率，每次45s-50s的旋涂时间，旋涂两次，涂层干结后厚度150nm-180nm的工艺，分别在步骤②获得的待用上ITO玻璃的上下两个表面及待用下ITO玻璃的上下表面全部进行旋涂处理，获得旋涂上ITO玻璃和旋涂下ITO玻璃；④Spin the sol solution C obtained in step ③ at a spin-coating speed of 1200rpm/min-1300rpm/min, each spin-coating time of 45s-50s, spin coating twice, the thickness of the coating after drying is 150nm-180nm, respectively In step ②, the upper and lower surfaces of the upper and lower ITO glass to be used and the upper and lower surfaces of the lower ITO glass to be used are all subjected to spin coating processing to obtain spin-coated ITO glass and spin-coated ITO glass;
　⑤将步骤④获得的旋涂上ITO玻璃和旋涂下ITO玻璃置于电阻炉中，采用460℃-480℃的温度烘烤80min-100min，获得蚀刻上ITO玻璃和蚀刻下ITO玻璃；　⑤ Put the spin-coated ITO glass and the spin-coated ITO glass obtained in step ④ in a resistance furnace, and bake at a temperature of 460℃-480℃ for 80min-100min to obtain etched ITO glass and etched ITO glass;
　⑥将阶段1）步骤①准备的[6，6]－苯基－C61－丁酸异甲酯与阶段1）步骤②准备的氯苯均匀混配成质量浓度20mg/ml的混液D；　⑥The [6,6]-phenyl-C61-isomethyl butyrate prepared in step 1) and the chlorobenzene prepared in step ② of step 1) are uniformly mixed into a mixture D with a mass concentration of 20mg/ml;
　⑦将阶段1）步骤①准备的硝酸钠、石墨粉混合均匀，加入混合粉末质量20倍的浓硫酸及阶段1）步骤①准备的高锰酸钾，边搅拌边冰浴2.5h-3h，然后静置8天-10天，在反应液内滴加阶段1）步骤②准备的过氧化氢水溶液至反应液不再产生气泡后，烘干水份，获得固体a，采用阶段1）步骤②准备的硝酸水溶液清洗固体a3次-5次，然后采用去离子水漂洗至PH=7，再次干燥，获得氧化石墨烯，将氧化石墨烯与去离子水混合并采用超声波细胞粉碎机超声震荡混配成质量浓度1.5mg/ml的氧化石墨烯分散液，采用氨水饱和溶液氨化处理氧化石墨烯分散液，获得氨化GO溶液；⑦Mix the sodium nitrate and graphite powder prepared in step 1) in step ①, add concentrated sulfuric acid 20 times the mass of the mixed powder and potassium permanganate prepared in step 1) in an ice bath for 2.5h-3h while stirring, then Let stand for 8-10 days, add dropwise the hydrogen peroxide solution prepared in step 1) in step ② until the reaction solution no longer generates bubbles, dry the water to obtain solid a, adopt step 1) step ② preparation Clean the solid a 3 times to 5 times with the nitric acid aqueous solution, then rinse with deionized water to PH=7, and dry again to obtain graphene oxide. Mix the graphene oxide with deionized water and use an ultrasonic cell pulverizer to ultrasonically vibrate. The graphene oxide dispersion with a mass concentration of 1.5 mg/ml is ammoniated with a saturated aqueous ammonia solution to obtain an ammoniated GO solution;
　⑧将阶段1）步骤①准备的CH3NH3PbI3与阶段1）步骤②准备的异丙醇混配成固含物浓度9mg/ml-12mg/ml的混液E；　⑧ Mix the CH3NH3PbI3 prepared in step 1) step ① with isopropanol prepared in step 1) step ② into a mixture E with a solid content of 9mg/ml-12mg/ml;
　⑨将步骤⑥获得的混液D与步骤⑦获得的氨化GO溶液按体积比1：（5-6）混合调配均匀后，将调配后的混合液在步骤⑤获得的蚀刻上ITO玻璃的下表面和蚀刻下ITO玻璃的上表面，以4200rpm/min-4500rpm/min的旋涂速率，45s-50s的旋涂时间均匀旋涂，然后将旋涂后的蚀刻上ITO玻璃和蚀刻下ITO玻璃置于真空环境内采用65℃-70℃完全烘干；再然后将烘干的上ITO玻璃和下ITO玻璃完全浸入步骤⑧获得的混液E中，保持25min-30min，然后在阶段1）步骤②准备的足量氮气保护下，采用65℃-70℃完全烘干然后炉冷至室温，获得终制上ITO玻璃和终制下ITO玻璃；⑨Mix the mixed solution D obtained in step ⑥ with the ammoniated GO solution obtained in step ⑦ according to the volume ratio of 1: (5-6). After the mixed solution is uniformly mixed, the lower surface of the ITO glass obtained in step ⑤ is etched with the mixed solution. And etch the upper surface of the ITO glass, spin-coating uniformly at a spin-coating rate of 4200rpm/min-4500rpm/min and a spin-coating time of 45s-50s, and then place the etched ITO glass and the etched ITO glass on the spin-coated Completely dry at 65℃-70℃ in a vacuum environment; then completely immerse the dried upper ITO glass and lower ITO glass in the mixture E obtained in step ⑧, keep it for 25min-30min, and then prepare in step 1) step ② Under the protection of a sufficient amount of nitrogen, complete drying at 65°C-70°C and then cool the furnace to room temperature to obtain the final upper ITO glass and the final lower ITO glass;
　　⑩将阶段1）步骤①准备的PEDOT：PSS水溶液以750rpm/min-800rpm/min的旋涂速率、32s-35s的旋涂时间分别旋涂在步骤⑨获得的终制上ITO玻璃的下表面和终制下ITO玻璃的上表面，然后将旋涂好的终制上ITO玻璃的下表面和终制下ITO玻璃的上表面在真空环境内紧密贴合，并在足量氮气保护下烘干35min-40min，随炉冷至室温后取出，获得的复合结构即为所需光感发电材料。⑩Spin-coat the PEDOT:PSS aqueous solution prepared in step 1) step ① at a spin-coating rate of 750rpm/min-800rpm/min and a spin-coating time of 32s-35s on the bottom surface and the final upper ITO glass obtained in step ⑨ Finish the upper surface of the ITO glass, and then the spin-coated lower surface of the final ITO glass and the upper surface of the final ITO glass are tightly attached in a vacuum environment, and dried under the protection of sufficient nitrogen for 35 minutes -40min, take it out after the furnace is cooled to room temperature, the obtained composite structure is the required photovoltaic power generation material.
　　本发明的整体光/热电能量转换率为26.0%-28.2%，能实现变害为利，平均可降低车内温度5℃-8℃，还具有自洁功能，下同。　　 The overall light/thermoelectric energy conversion rate of the present invention is 26.0%-28.2%, which can turn harm into profit, reduce the temperature in the car by 5°C-8°C on average, and has a self-cleaning function, the same below.
本发明的实施方式Embodiments of the invention
整体与实施例1一致，差异之处在于：The whole is consistent with Example 1, the differences are:
　其中，光感发电材料的制造方法包括以下步骤：　Among them, the manufacturing method of the photovoltaic power generation material includes the following steps:
　1）原材料准备　1) Preparation of raw materials
①原材料准备：按重量份准备钛酸四丁酯50Kg、二乙醇胺12Kg、溶质质量分数1.5%的PEDOT：PSS水溶液70Kg、[6，6]－苯基－C61－丁酸异甲酯18Kg、高锰酸钾48Kg、足量弧实施例3：①Preparation of raw materials: prepare tetrabutyl titanate 50Kg, diethanolamine 12Kg, and 1.5% solute PEDOT: PSS aqueous solution 70Kg, [6,6]-phenyl-C61-isomethyl butyrate 18Kg, high Potassium manganate 48Kg, sufficient arc Example 3:
整体与实施例1一致，差异之处在于：The whole is consistent with Example 1, the differences are:
其中，光感发电材料的制造方法包括以下步骤：Among them, the manufacturing method of the photovoltaic power generation material includes the following steps:
1）原材料准备1) Preparation of raw materials
①原材料准备：按重量份准备钛酸四丁酯55Kg、二乙醇胺15Kg、溶质质量分数1.5%的PEDOT：PSS水溶液65Kg、[6，6]－苯基－C61－丁酸异甲酯16Kg、高锰酸钾45Kg、足量弧形ITO玻璃板、硝酸钠7Kg、石墨粉10Kg、CH3NH3PbI3 12Kg、足量氨水饱和溶液；形ITO玻璃板、硝酸钠9Kg、石墨粉12Kg、CH3NH3PbI3 15Kg、足量氨水饱和溶液；① Preparation of raw materials: prepare tetrabutyl titanate 55Kg, diethanolamine 15Kg, 1.5% solute mass fraction of PEDOT: PSS aqueous solution 65Kg, [6,6]-phenyl-C61-isomethyl butyrate 16Kg, high Potassium manganate 45Kg, sufficient curved ITO glass plate, 7Kg sodium nitrate, graphite powder 10Kg, CH3NH3PbI3 12Kg, sufficient ammonia saturated solution; shaped ITO glass plate, sodium nitrate 9Kg, graphite powder 12Kg, CH3NH3PbI3 15Kg, sufficient ammonia saturated Solution
工业实用性Industrial applicability
本发明具有集成光电转换与热电转换功能、总效率高、车内温降好、车体结构变动少的特性。The invention has the characteristics of integrated photoelectric conversion and thermoelectric conversion functions, high total efficiency, good temperature drop in the vehicle, and little change in the structure of the vehicle body.
序列表自由内容Sequence Listing Free Content
对所公开的实施例的上述说明，仅为了使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The above description of the disclosed embodiments is only to enable those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown in this document, but should conform to the widest scope consistent with the principles and novel features disclosed in this document.

Claims (1)

  1. 一种汽车中控台盖板用双功能复合发电材料，其特征在于：该复合发电材料分为光感发电材料和热感发电材料两个部分，其中光感发电材料由上至下设置有上衬层、上ITO玻璃、功能层、下ITO玻璃、底衬层共五层；热感发电材料具体为热触面与底衬层下表面贴合的20-25层堆栈的石墨烯热电发生器，该石墨烯热电发生器的冷触面设置在雨刷水箱的底面；A dual-function composite power generation material for an automobile center console cover, which is characterized in that the composite power generation material is divided into two parts: a photovoltaic power generation material and a thermal power generation material. The photovoltaic power generation material is arranged from top to bottom. There are five layers of lining layer, upper ITO glass, functional layer, lower ITO glass, and backing layer; the thermal power generation material is specifically a graphene thermoelectric generator with 20-25 layers stacked on the thermal contact surface and the bottom surface of the backing layer. , The cold contact surface of the graphene thermoelectric generator is set on the bottom surface of the wiper water tank;
    其中，光感发电材料的制造方法包括以下步骤：Among them, the manufacturing method of the photovoltaic power generation material includes the following steps:
    　1）原材料准备　1) Preparation of raw materials
    　　①原材料准备：按重量份准备钛酸四丁酯50份-55份、二乙醇胺12份-15份、溶质质量分数1.5%的PEDOT：PSS水溶液65份-70份、[6，6]－苯基－C61－丁酸异甲酯16份-18份、高锰酸钾45份-48份、二甲基亚砜50份-55份、足量弧形ITO玻璃板、硝酸钠7份-9份、石墨粉10份-12份、CH3NH3PbI3 12份-15份、足量氨水饱和溶液；①Preparation of raw materials: prepare 50-55 parts of tetrabutyl titanate, 12-15 parts of diethanolamine, 1.5% solute mass fraction of PEDOT: PSS aqueous solution 65-70 parts, [6,6]-benzene by weight Base-C61-isomethyl butyrate 16-18 parts, potassium permanganate 45-48 parts, dimethyl sulfoxide 50-55 parts, sufficient curved ITO glass plate, sodium nitrate 7-9 parts Parts, 10 parts to 12 parts of graphite powder, 12 parts to 15 parts of CH3NH3PbI3, enough saturated ammonia solution;
    　　②辅材准备：准备足量无水乙醇、足量乙醚、足量N,N二甲基二酰胺、足量氮气、足量氯苯、足量异丙醇、足量锌粉、足量溶质质量分数20%的盐酸水溶液、足量去离子水、足量溶质质量分数10%的硝酸水溶液、足量浓硫酸、足量质量分数20%过氧化氢水溶液；② Preparation of auxiliary materials: prepare enough absolute ethanol, enough ether, enough N,N dimethyl diamide, enough nitrogen, enough chlorobenzene, enough isopropanol, enough zinc powder, enough solute 20% hydrochloric acid aqueous solution, sufficient deionized water, sufficient nitric acid aqueous solution with 10% mass fraction of solute, sufficient concentrated sulfuric acid, sufficient mass fraction of 20% hydrogen peroxide aqueous solution;
    　　2）受光区制造方法　　2) Manufacturing method of light receiving area
    　　①准备两块阶段1）步骤①准备的弧形ITO玻璃板，将阶段1）步骤②准备的锌粉分别均匀涂抹在两块ITO玻璃板的上表面上，涂抹至目视完全覆盖，然后将阶段1）步骤②准备的盐酸水溶液缓慢滴加在锌粉上直至锌粉完全润湿，保持2min-3min，将盐酸水溶液和锌粉采用乙醇和去离子水分别清洗至完全清洗干净，获得两块单面润蚀ITO玻璃；①Prepare two curved ITO glass plates prepared in step 1), and apply the zinc powder prepared in step 1) step ② to the upper surfaces of the two ITO glass plates evenly. Stage 1) The hydrochloric acid aqueous solution prepared in step ② is slowly dripped on the zinc powder until the zinc powder is completely wetted, and kept for 2min-3min. The hydrochloric acid aqueous solution and the zinc powder are washed with ethanol and deionized water respectively until they are completely cleaned to obtain two pieces Etching ITO glass on one side;
    　　②将步骤①获得的单面润蚀ITO玻璃翻转，然后重复一次步骤①，获得两块双面润蚀ITO玻璃，即为待用上ITO玻璃和待用下ITO玻璃；　　②Invert the single-sided etched ITO glass obtained in step ①, and then repeat step ① to obtain two double-sided etched ITO glasses, namely the upper ITO glass to be used and the lower ITO glass to be used;
    　　③将阶段1）步骤①准备的钛酸四丁酯、二乙醇胺与按重量份计的150份-160份乙醇混合均匀，以600rpm/min-800rpm/min的速率搅拌1.5h-2h，获得混液A；将按重量份计的15份-17份去离子水与75份-80份乙醇混配成醇水混溶液，即为混液B；将混液A和混液B混合并搅拌均匀后，获得混液C，将混液C在密闭环境内静置28h-30h，混液C溶胶化，获得溶胶液C；③Mix the tetrabutyl titanate and diethanolamine prepared in step 1) step ① with 150 to 160 parts by weight of ethanol, and stir for 1.5h-2h at a rate of 600rpm/min-800rpm/min to obtain a mixed solution A; Mix 15-17 parts by weight of deionized water and 75-80 parts of ethanol to form an alcohol-water mixed solution, which is mixed liquid B; mix and stir evenly with mixed liquid A and mixed liquid B to obtain mixed liquid C, the mixed liquid C is allowed to stand for 28h-30h in a closed environment, and the mixed liquid C is solized to obtain the sol liquid C;
    　　④将步骤③获得的溶胶液C以1200rpm/min-1300rpm/min的旋涂速率，每次45s-50s的旋涂时间，旋涂两次，涂层干结后厚度150nm-180nm的工艺，分别在步骤②获得的待用上ITO玻璃的上下两个表面及待用下ITO玻璃的上下表面全部进行旋涂处理，获得旋涂上ITO玻璃和旋涂下ITO玻璃；④Spin the sol solution C obtained in step ③ at a spin-coating speed of 1200rpm/min-1300rpm/min, each spin-coating time of 45s-50s, spin coating twice, the thickness of the coating after drying is 150nm-180nm, respectively In step ②, the upper and lower surfaces of the upper and lower ITO glass to be used and the upper and lower surfaces of the lower ITO glass to be used are all subjected to spin coating processing to obtain spin-coated ITO glass and spin-coated ITO glass;
    　　⑤将步骤④获得的旋涂上ITO玻璃和旋涂下ITO玻璃置于电阻炉中，采用460℃-480℃的温度烘烤80min-100min，获得蚀刻上ITO玻璃和蚀刻下ITO玻璃；　　⑤ Put the spin-coated ITO glass and spin-coated ITO glass obtained in step ④ in a resistance furnace, and bake at a temperature of 460℃-480℃ for 80min-100min to obtain etched ITO glass and etched ITO glass;
    　　⑥将阶段1）步骤①准备的[6，6]－苯基－C61－丁酸异甲酯与阶段1）步骤②准备的氯苯均匀混配成质量浓度20mg/ml的混液D；　　⑥ The [6,6]-phenyl-C61-isomethyl butyrate prepared in step 1) step ① and the chlorobenzene prepared in step 1) step ② are uniformly mixed into a mixture D with a mass concentration of 20 mg/ml;
    　　⑦将阶段1）步骤①准备的硝酸钠、石墨粉混合均匀，加入混合粉末质量20倍的浓硫酸及阶段1）步骤①准备的高锰酸钾，边搅拌边冰浴2.5h-3h，然后静置8天-10天，在反应液内滴加阶段1）步骤②准备的过氧化氢水溶液至反应液不再产生气泡后，烘干水份，获得固体a，采用阶段1）步骤②准备的硝酸水溶液清洗固体a3次-5次，然后采用去离子水漂洗至PH=7，再次干燥，获得氧化石墨烯，将氧化石墨烯与去离子水混合并采用超声波细胞粉碎机超声震荡混配成质量浓度1.5mg/ml的氧化石墨烯分散液，采用氨水饱和溶液氨化处理氧化石墨烯分散液，获得氨化GO溶液；⑦Mix the sodium nitrate and graphite powder prepared in step 1) in step ①, add concentrated sulfuric acid 20 times the mass of the mixed powder and potassium permanganate prepared in step 1) in an ice bath for 2.5h-3h while stirring, then Let stand for 8-10 days, add dropwise the hydrogen peroxide solution prepared in step 1) in step ② until the reaction solution no longer generates bubbles, dry the water to obtain solid a, adopt step 1) step ② preparation Clean the solid a 3 times to 5 times with the nitric acid aqueous solution, then rinse with deionized water to PH=7, and dry again to obtain graphene oxide. Mix the graphene oxide with deionized water and use an ultrasonic cell pulverizer to ultrasonically vibrate. The graphene oxide dispersion with a mass concentration of 1.5 mg/ml is ammoniated with a saturated aqueous ammonia solution to obtain an ammoniated GO solution;
    　　⑧将阶段1）步骤①准备的CH3NH3PbI3与阶段1）步骤②准备的异丙醇混配成固含物浓度9mg/ml-12mg/ml的混液E；　　⑧ Mix the CH3NH3PbI3 prepared in step 1) step ① with the isopropanol prepared in step 1) step ② into a mixture E with a solid content concentration of 9mg/ml-12mg/ml;
    　　⑨将步骤⑥获得的混液D与步骤⑦获得的氨化GO溶液按体积比1：（5-6）混合调配均匀后，将调配后的混合液在步骤⑤获得的蚀刻上ITO玻璃的下表面和蚀刻下ITO玻璃的上表面，以4200rpm/min-4500rpm/min的旋涂速率，45s-50s的旋涂时间均匀旋涂，然后将旋涂后的蚀刻上ITO玻璃和蚀刻下ITO玻璃置于真空环境内采用65℃-70℃完全烘干；再然后将烘干的上ITO玻璃和下ITO玻璃完全浸入步骤⑧获得的混液E中，保持25min-30min，然后在阶段1）步骤②准备的足量氮气保护下，采用65℃-70℃完全烘干然后炉冷至室温，获得终制上ITO玻璃和终制下ITO玻璃；⑨Mix the mixed solution D obtained in step ⑥ with the ammoniated GO solution obtained in step ⑦ according to the volume ratio of 1: (5-6). After the mixed solution is uniformly mixed, the lower surface of the ITO glass obtained in step ⑤ is etched with the mixed solution. And etch the upper surface of the ITO glass, spin-coating uniformly at a spin-coating rate of 4200rpm/min-4500rpm/min and a spin-coating time of 45s-50s, and then place the etched ITO glass and the etched ITO glass on the spin-coated Completely dry at 65℃-70℃ in a vacuum environment; then completely immerse the dried upper ITO glass and lower ITO glass in the mixture E obtained in step ⑧, keep it for 25min-30min, and then prepare in step 1) step ② Under the protection of a sufficient amount of nitrogen, complete drying at 65°C-70°C and then cool the furnace to room temperature to obtain the final upper ITO glass and the final lower ITO glass;
    　　⑩将阶段1）步骤①准备的PEDOT：PSS水溶液以750rpm/min-800rpm/min的旋涂速率、32s-35s的旋涂时间分别旋涂在步骤⑨获得的终制上ITO玻璃的下表面和终制下ITO玻璃的上表面，然后将旋涂好的终制上ITO玻璃的下表面和终制下ITO玻璃的上表面在真空环境内紧密贴合，并在足量氮气保护下烘干35min-40min，随炉冷至室温后取出，获得的复合结构即为所需光感发电材料。⑩Spin-coat the PEDOT:PSS aqueous solution prepared in step 1) step ① at a spin-coating rate of 750rpm/min-800rpm/min and a spin-coating time of 32s-35s on the bottom surface and the final upper ITO glass obtained in step ⑨ Finish the upper surface of the ITO glass, and then the spin-coated lower surface of the final ITO glass and the upper surface of the final ITO glass are tightly attached in a vacuum environment, and dried under the protection of sufficient nitrogen for 35 minutes -40min, take it out after the furnace is cooled to room temperature, the obtained composite structure is the required photovoltaic power generation material.
PCT/CN2019/096370 2019-07-09 2019-07-17 Bifunctional composite power generation material for use in center console cover of automobile, and manufacturing method therefor WO2021003764A1 (en)

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