技术领域Technical Field
本发明属于辐射制冷材料技术领域，具体涉及一种抗老化辐射制冷透明薄膜及其制备方法与应用。The invention belongs to the technical field of radiation refrigeration materials, and in particular relates to an anti-aging radiation refrigeration transparent film and a preparation method and application thereof.
背景技术Background Art
近年来，随着全球温室效应不断加剧，环境和人类健康受到的严重影响日益凸显，例如极端天气事件频发，海平面上升，生态系统受到破坏。因此绿色清洁材料的发展成为当前研究的焦点，传统的降温方式(如风扇和空调)在运行中不仅消耗电力资源，还会产生大量温室气体，加剧了温室效应的恶化。因此，寻求环保清洁的降温方法是目前亟待解决的问题。In recent years, as the global greenhouse effect continues to intensify, the serious impact on the environment and human health has become increasingly prominent, such as frequent extreme weather events, rising sea levels, and damaged ecosystems. Therefore, the development of green and clean materials has become the focus of current research. Traditional cooling methods (such as fans and air conditioners) not only consume electricity resources during operation, but also produce a large amount of greenhouse gases, exacerbating the worsening of the greenhouse effect. Therefore, seeking environmentally friendly and clean cooling methods is an urgent problem to be solved.
窗户的被动冷却可以有效地降低建筑或汽车内部空调功耗，其工作原理是减少太阳辐射热量透射的同时增大内部热量的释放。根据基尔霍夫热力学定律，在热平衡条件下，物体对热辐射的吸收比恒等于同温度下的辐射率，辐射制冷可以将常温物体的热量以中红外波段电磁波的形式通过大气透明窗口(8-13μm)辐射到温度为3K的外太空，实现零功耗的降温过程。另外，对于窗户等需要采光的应用场所中，准确的调控太阳光谱在可见光波段(450-780nm)及近红外波段(780-2100nm)的透过率与反射率可以有效实现降温与采光的平衡。因此，将太阳能光谱选择性透射与辐射冷却相结合可以最大化窗户的降温性能，且没有任何能源的消耗与排放，在汽车、建筑窗户等应用领域具有广阔的应用前景。Passive cooling of windows can effectively reduce the power consumption of air conditioning in buildings or cars. Its working principle is to reduce the transmission of solar radiation heat while increasing the release of internal heat. According to Kirchhoff's laws of thermodynamics, under thermal equilibrium conditions, the absorption ratio of an object to thermal radiation is always equal to the emissivity at the same temperature. Radiative cooling can radiate the heat of a normal temperature object in the form of electromagnetic waves in the mid-infrared band through an atmospheric transparent window (8-13μm) to the outer space with a temperature of 3K, achieving a zero-power cooling process. In addition, for application places such as windows that require lighting, accurate regulation of the transmittance and reflectivity of the solar spectrum in the visible light band (450-780nm) and near-infrared band (780-2100nm) can effectively achieve a balance between cooling and lighting. Therefore, combining the selective transmission of the solar spectrum with radiative cooling can maximize the cooling performance of windows without any energy consumption and emissions, and has broad application prospects in application fields such as automobiles and building windows.
公开号为CN117467320A的专利文献公开了一种基于氮化物颜料的日间辐射制冷涂料及其制备方法，该涂料的制备原材料包括氮化物颜料、填料、树脂乳液、助剂以及水。该发明的基于氮化物颜料的日间辐射制冷涂料具有极高太阳光反射比和半球发射率，因而即便在阳光强烈的日间,也具有优异的辐射制冷性能，使被涂敷物体的温度低于环境温度以下。将该发明的高太阳光反射比的辐射制冷涂料用于涂覆在建筑物或其他露天设施表面，可以降低商业和住宅建筑物及其他户外设施用于制冷的能耗。然而，该方法制备得到的薄膜在太阳光波段包括可见光的高反射率，限制了其在车窗及建筑窗户等场景的应用。The patent document with publication number CN117467320A discloses a daytime radiation cooling paint based on nitride pigments and a preparation method thereof, wherein the raw materials for preparing the paint include nitride pigments, fillers, resin emulsions, additives and water. The daytime radiation cooling paint based on nitride pigments of the invention has extremely high solar reflectance and hemispherical emissivity, so that even in the daytime with strong sunlight, it has excellent radiation cooling performance, making the temperature of the coated object lower than the ambient temperature. The radiation cooling paint with high solar reflectance of the invention is used for coating on the surface of buildings or other open-air facilities, which can reduce the energy consumption of commercial and residential buildings and other outdoor facilities for cooling. However, the film prepared by this method has a high reflectance in the sunlight band, including visible light, which limits its application in scenes such as car windows and building windows.
公开号为CN116394610A的专利文献公开了一种柔性透明辐射制冷窗材料，由中红外发射层、近红外反射层和可见光增透层组成；所述中红外发射层为高分子聚合物材料，厚度为50-300μm，实现中红外波段吸收/发射；所述近红外反射层材料为银，厚度为10nm，实现近红外0.8-2.5μm太阳光谱的反射；所述可见光增透层为高分子聚合物材料，厚度为50-300μm，通过构造聚合物-金属-聚合物(PMP)结构，实现可见光透射、近红外高反射的功能；所述材料在0.4-0.8μm太阳辐射可见光波段的平均透射率大于0.6,在0.8-2.5μm太阳辐射近红外波段平均反射率大于0.8，在8-13μm“大气窗口”的平均发射率大于0.95。然而，由于其涉及到的有机材料在长时间太阳照射下会发生老化，导致降温及采光性能降低。The patent document with publication number CN116394610A discloses a flexible transparent radiation refrigeration window material, which is composed of a mid-infrared emission layer, a near-infrared reflection layer and a visible light transmittance-enhancing layer; the mid-infrared emission layer is a high molecular polymer material with a thickness of 50-300 μm, which realizes absorption/emission in the mid-infrared band; the near-infrared reflection layer material is silver with a thickness of 10 nm, which realizes reflection of the near-infrared 0.8-2.5 μm solar spectrum; the visible light transmittance-enhancing layer is a high molecular polymer material with a thickness of 50-300 μm, and realizes the functions of visible light transmission and near-infrared high reflection by constructing a polymer-metal-polymer (PMP) structure; the material has an average transmittance of greater than 0.6 in the visible light band of 0.4-0.8 μm solar radiation, an average reflectivity of greater than 0.8 in the near-infrared band of 0.8-2.5 μm solar radiation, and an average emissivity of greater than 0.95 in the 8-13 μm "atmospheric window". However, the organic materials involved will age under long-term sunlight exposure, resulting in reduced cooling and lighting performance.
公开号为CN114714692A的专利文献公开一种基于仿生玫瑰花瓣微纳结构的可见-近红外分频型辐射制冷薄膜及其制备方法与应用，所述薄膜，包括自上而下设置的仿生玫瑰花瓣结构的透明仿生微纳结构层和多层薄膜结构层，透明仿生微纳结构层表面呈阵列分布有第一锥体微纳结构；第一锥体微纳结构的表面呈阵列分布有第二锥体微纳结构。本发明实现了辐射制冷薄膜对太阳辐射能量选择性透过，实现可见-近红外波段分频功能和大气窗口高发射性能，能够兼顾采光和制冷性能，从而拓宽了辐射制冷材料的适用范围。然而，高的结构复杂度及精度要求使其加工成本大幅度提高，难以大规模生产。The patent document with the publication number CN114714692A discloses a visible-near-infrared frequency division type radiation cooling film based on a bionic rose petal micro-nano structure and its preparation method and application. The film includes a transparent bionic micro-nano structure layer and a multilayer film structure layer of a bionic rose petal structure arranged from top to bottom. The surface of the transparent bionic micro-nano structure layer is distributed in an array with a first cone micro-nano structure; the surface of the first cone micro-nano structure is distributed in an array with a second cone micro-nano structure. The present invention realizes the selective transmission of solar radiation energy by the radiation cooling film, realizes the visible-near-infrared band frequency division function and the high emission performance of the atmospheric window, can take into account both lighting and cooling performance, thereby broadening the scope of application of radiation cooling materials. However, the high structural complexity and precision requirements greatly increase its processing cost, making it difficult to produce on a large scale.
虽然现有技术对辐射制冷薄膜进行了较多的研究，但现有的辐射制冷薄膜仍存在可见光低透过率、易老化、制备方法复杂等问题。因此，提供一种结构简单、在可见光波段透过率高的抗老化辐射制冷薄膜，以满足汽车及建筑等对采光和降温兼具需求场所的应用具有重要的意义。Although the prior art has conducted a lot of research on radiative cooling films, the existing radiative cooling films still have problems such as low visible light transmittance, easy aging, and complex preparation methods. Therefore, it is of great significance to provide an anti-aging radiative cooling film with a simple structure and high transmittance in the visible light band to meet the application requirements of automobiles and buildings for both lighting and cooling.
发明内容Summary of the invention
本发明的目的在于提供一种抗老化辐射制冷透明薄膜及其制备方法与应用，所述抗老化辐射制冷透明薄膜可在反射太阳光热量的同时向外辐射热量，且具有较高的可见光透过率，兼具采光与被动冷却的能力，在汽车车窗、建筑窗户、手机屏幕等户外场所等具有广阔的应用场景。The purpose of the present invention is to provide an anti-aging radiant cooling transparent film and a preparation method and application thereof. The anti-aging radiant cooling transparent film can radiate heat outward while reflecting the heat of sunlight, and has a high visible light transmittance, and has the ability of both lighting and passive cooling. It has a wide range of application scenarios in outdoor places such as car windows, building windows, mobile phone screens, etc.
本发明第一个方面提供了一种抗老化辐射制冷透明薄膜，包括：(Ⅰ)太阳光反射层；或者(Ⅱ)太阳光反射层和位于所述太阳光反射层上的辐射层，所述抗老化辐射制冷透明薄膜在中红外波段的发射率大于30％，在近红外波段的反射率大于60％，在可见光波段的透明度大于30％。The first aspect of the present invention provides an anti-aging radiative cooling transparent film, comprising: (I) a sunlight reflecting layer; or (II) a sunlight reflecting layer and a radiation layer located on the sunlight reflecting layer, wherein the anti-aging radiative cooling transparent film has an emissivity greater than 30% in the mid-infrared band, a reflectivity greater than 60% in the near-infrared band, and a transparency greater than 30% in the visible light band.
本发明的抗老化辐射制冷透明薄膜既可以只包括太阳光反射层，也可以包括太阳光反射层和辐射层。优选地，当抗老化辐射制冷透明薄膜包括反射层与辐射层时，所述的太阳光反射层在近红外波段的反射率大于60％，在可见光波段透明度大于30％；所述辐射层在中红外波段发射率大于30％。若反射层材料可满足辐射需求则无需添加辐射层。The anti-aging radiation cooling transparent film of the present invention may include only a sunlight reflecting layer or a sunlight reflecting layer and a radiation layer. Preferably, when the anti-aging radiation cooling transparent film includes a reflecting layer and a radiation layer, the reflectivity of the sunlight reflecting layer in the near-infrared band is greater than 60%, and the transparency in the visible light band is greater than 30%; the emissivity of the radiation layer in the mid-infrared band is greater than 30%. If the reflective layer material can meet the radiation requirements, there is no need to add a radiation layer.
本发明的抗老化辐射制冷透明薄膜结合了材料在不同波段范围内的光学性质与光学结构对光谱调节的特性，可以实现反射太阳光近红外波段热量的同时具有高可见光透过率，并且可以被动向外辐射热量。The anti-aging radiation cooling transparent film of the present invention combines the optical properties of the material in different wavelength ranges with the characteristics of the optical structure for spectrum regulation, and can reflect the heat of the near-infrared band of sunlight while having a high visible light transmittance, and can passively radiate heat outward.
优选地，所述的太阳光反射层的材料为无机材料，可以使薄膜具有良好的抗老化特性。进一步优选地，所述的无机材料选择如Ag、Al、ITO、SiO2、Si3N4、TiO2、Al2O3等常见材料，可进一步降低加工成本与工艺要求。Preferably, the sunlight reflecting layer is made of inorganic materials, which can make the film have good anti-aging properties. Further preferably, the inorganic materials are selectedfrom common materials such as Ag, Al, ITO,SiO2 ,Si3N4 ,TiO2 ,Al2O3, etc., which can further reduce processing costs and process requirements.
优选地，所述的太阳光反射层的结构为单层或者多层薄膜结构。Preferably, the structure of the sunlight reflecting layer is a single-layer or multi-layer thin film structure.
优选地，所述的太阳光反射层单层薄膜的厚度为1nm～10μm，太阳光反射层整体厚度小于1000μm。更优选地，所述的太阳光反射层单层薄膜的厚度0.01～10μm。Preferably, the thickness of the single-layer film of the sunlight reflection layer is 1 nm to 10 μm, and the overall thickness of the sunlight reflection layer is less than 1000 μm. More preferably, the thickness of the single-layer film of the sunlight reflection layer is 0.01 to 10 μm.
优选地，所述的多层薄膜结构由折射率不同的无机材料薄膜组合排列而成，相邻薄膜之间的折射率在近红外波段范围内差值至少>0.1。折射率的差距可以更精准地对其光谱转换波长进行调节。Preferably, the multilayer film structure is composed of inorganic material films with different refractive indices, and the difference in refractive index between adjacent films in the near-infrared band is at least >0.1. The difference in refractive index can more accurately adjust the spectral conversion wavelength.
优选地，所述的多层薄膜结构为周期结构。周期结构的反射层可实现可见光与近红外光之间透过率与反射率的切换，在保证可见光透明度的同时阻挡近红外光对窗户与室内进行加热，通过调节重复结构每层的厚度可以对转换波长进行精准调控，并且其反射率可以通过改变总层数进行优化。Preferably, the multilayer film structure is a periodic structure. The reflective layer of the periodic structure can realize the switching of transmittance and reflectance between visible light and near-infrared light, while ensuring the transparency of visible light, blocking near-infrared light from heating the windows and the room. By adjusting the thickness of each layer of the repeated structure, the conversion wavelength can be precisely controlled, and its reflectivity can be optimized by changing the total number of layers.
优选地，所述的周期结构的周期数>2。通过控制周期结构的周期数可以进一步提升薄膜的透过与反射性能。Preferably, the period number of the periodic structure is greater than 2. The transmittance and reflection properties of the film can be further improved by controlling the period number of the periodic structure.
优选地，所述的周期结构为布拉格反射镜结构(DBR)或双曲超材料结构(HMM)。此结构的反射层可以实现可见光透过率与近红外反射率交界波长处更加显著的切换。Preferably, the periodic structure is a Bragg reflector structure (DBR) or a hyperbolic metamaterial structure (HMM). The reflective layer of this structure can achieve a more significant switching at the boundary wavelength between visible light transmittance and near-infrared reflectance.
优选地，所述的布拉格反射镜结构每周期为Si3N4薄膜与SiO2薄膜组合，或者SiO2薄膜与TiO2薄膜组合，所述Si3N4薄膜与SiO2薄膜组合结构中，Si3N4薄膜的厚度为10～600nm，SiO2薄膜的厚度为10～600nm；所述SiO2薄膜与TiO2薄膜组合中，SiO2薄膜的厚度为10～600nm，TiO2薄膜的厚度为10～600nm。布拉格反射镜中各个薄膜的厚度等于入射光在相应层的1/4等效波长。Preferably, each period of the Bragg reflector structure is a combination of Si3 N4 film and SiO2 film, or a combination of SiO2 film and TiO2 film. In the combination of Si3 N4 film and SiO2 film, the thickness of Si3 N4 film is 10-600nm, and the thickness of SiO2 film is 10-600nm; in the combination of SiO2 film and TiO2 film, the thickness of SiO2 film is 10-600nm, and the thickness of TiO2 film is 10-600nm. The thickness of each film in the Bragg reflector is equal to 1/4 of the equivalent wavelength of the incident light in the corresponding layer.
优选地，所述的双曲超材料结构每周期为Ag薄膜与SiO2薄膜组合，所述Ag薄膜与SiO2薄膜组合中，Ag薄膜的厚度为2～40nm，SiO2薄膜的厚度为10～600nm。此双曲材料结构中每层膜的厚度利用双曲超材料等效介电理论(EMT)进行计算，等效介电常数为0对应的波长应为可见光与近红外交界处(700～800nm)。Preferably, each period of the hyperbolic metamaterial structure is a combination of an Ag film andaSiO2 film, wherein the thickness of the Ag film is 2 to 40 nm, and the thickness of theSiO2 film is 10 to 600 nm. The thickness of each film in the hyperbolic material structure is calculated using the hyperbolic metamaterial equivalent dielectric theory (EMT), and the wavelength corresponding to the equivalent dielectric constant of 0 should be the boundary between visible light and near-infrared (700 to 800 nm).
优选地，所述的双曲超材料结构每周期为Ag薄膜和ITO薄膜组合，所述Ag薄膜的厚度为2～40nm，所述ITO薄膜的厚度为10～600nm。此双曲材料结构中每层膜的厚度利用双曲超材料等效介电理论(EMT)进行计算，等效介电常数为0对应的波长应为可见光与近红外交界处。该结构在良好的降温性能与透明度的基础上，选择导电性良好且透明的材料用于反射层结构的设计。相比于原有几乎绝缘反射层结构，具有导电性能的无机材料可以提升窗户整体导电性能，从而使得制备的抗老化辐射制冷透明薄膜具有电控除霜、除雾能力。Preferably, each period of the hyperbolic metamaterial structure is a combination of an Ag film and an ITO film, the thickness of the Ag film is 2 to 40 nm, and the thickness of the ITO film is 10 to 600 nm. The thickness of each film layer in this hyperbolic material structure is calculated using the hyperbolic metamaterial equivalent dielectric theory (EMT), and the wavelength corresponding to the equivalent dielectric constant of 0 should be at the interface between visible light and near-infrared. Based on good cooling performance and transparency, this structure selects materials with good conductivity and transparency for the design of the reflective layer structure. Compared with the original almost insulating reflective layer structure, inorganic materials with conductive properties can improve the overall conductivity of the window, so that the prepared anti-aging radiation refrigeration transparent film has the ability of electrically controlled defrosting and defogging.
优选地，所述的辐射层在中红外波段的发射率大于40％。更优选地，所述的辐射层在中红外波段发射率大于50％。Preferably, the emissivity of the radiation layer in the mid-infrared band is greater than 40%. More preferably, the emissivity of the radiation layer in the mid-infrared band is greater than 50%.
优选地，所述辐射层材料为无机材料或者经过优化抗老化处理的有机材料，可提升薄膜抗老化及耐刮花性能。进一步优选地，所述的辐射层选择中红外具有良好吸收率的材料，可提升薄膜辐射冷却能力，例如InAsSb、ZnTe、Ge等无机材料或经抗老化处理的PDMS、PMMA等有机材料。更优选地，所述辐射层选择SiO2、Si3N4、Al2O3等在可见光波段具有良好透明度且在中红外波段具有良好发射率的材料。Preferably, the radiation layer material is an inorganic material or an organic material that has been optimized for anti-aging treatment, which can improve the film's anti-aging and scratch resistance. Further preferably, the radiation layer is made of a material with good mid-infrared absorptivity, which can improve the film's radiation cooling capacity, such as InAsSb, ZnTe, Ge and other inorganic materials or PDMS, PMMA and other organic materials that have been treated for anti-aging. More preferably, the radiation layer is made of SiO2 , Si3 N4 , Al2 O3 and other materials that have good transparency in the visible light band and good emissivity in the mid-infrared band.
优选地，所述的辐射层结构为单层或者多层薄膜结构。Preferably, the radiation layer structure is a single-layer or multi-layer thin film structure.
优选地，所述的辐射层单层薄膜厚度为0.01～500μm，辐射层整体厚度小于5000μm。辐射层厚度可以同时兼具太阳光辐照波段的透明度与大气透明窗口的辐射降温性能，具体厚度可根据实际材料及加工工艺进行调整，在对采光与降温兼具需求的场所具有广泛的应用前景。更优选地，所述的辐射层薄膜单层厚度为0.1-200μm，辐射层整体厚度小于2000μm。Preferably, the thickness of the single-layer film of the radiation layer is 0.01-500μm, and the overall thickness of the radiation layer is less than 5000μm. The thickness of the radiation layer can have both the transparency of the solar radiation band and the radiation cooling performance of the atmospheric transparent window. The specific thickness can be adjusted according to the actual material and processing technology, and has a wide range of application prospects in places that require both lighting and cooling. More preferably, the thickness of the single-layer film of the radiation layer is 0.1-200μm, and the overall thickness of the radiation layer is less than 2000μm.
所述的辐射层结构可选择相同或者不同的材料堆叠而成，以便进行参数优化及性能提升，若反射层辐射能力满足需求则无需添加辐射层。优选地，当所述辐射层为多层薄膜结构时，所述的多层薄膜结构的最外层为Si3N4薄膜，内层为SiO2薄膜和/或Al2O3薄膜，其中，所述Si3N4薄膜厚度为30～6000nm；SiO2薄膜厚度为30～6000nm；Al2O3薄膜厚度为30～6000nm。当Si3N4薄膜为辐射层最外层时，辐射层的辐射效果相较其它薄膜在外层时可提升5％左右。The radiation layer structure can be stacked with the same or different materials to optimize parameters and improve performance. If the radiation capacity of the reflective layer meets the requirements, there is no need to add a radiation layer. Preferably, when the radiation layer is a multi-layer thin film structure, the outermost layer of the multi-layer thin film structure is a Si3 N4 film, and the inner layer is a SiO2 film and/or an Al2 O3 film, wherein the thickness of the Si3 N4 film is 30 to 6000nm; the thickness of the SiO2 film is 30 to 6000nm; the thickness of the Al2 O3 film is 30 to 6000nm. When the Si3 N4 film is the outermost layer of the radiation layer, the radiation effect of the radiation layer can be improved by about 5% compared with other films in the outer layer.
本发明通过对薄膜的结构进行设计，可将其中红外波段的发射率、近红外波段的反射率以及可见光波段的透明度提高到80％以上，甚至高达90％以上，接近100％。The present invention can improve the emissivity in the infrared band, the reflectivity in the near-infrared band and the transparency in the visible light band to more than 80%, even up to more than 90%, close to 100%, by designing the structure of the film.
本发明的抗老化辐射制冷透明薄膜可通过常规方法制备得到。将基底(硅片或玻璃板)放入仪器中，利用薄膜沉积技术进行逐层制备。例如SiO2、TiO2和ITO薄膜可通过物理气相沉积(PVD)、化学气相沉积(CVD)或原子层沉积(ALD)等工艺进行制备；Ag薄膜可以通过溶胶-凝胶法、CVD法、溅射法等工艺进行制备。The anti-aging radiation cooling transparent film of the present invention can be prepared by conventional methods. The substrate (silicon wafer or glass plate) is placed in an instrument and prepared layer by layer using thin film deposition technology. For example,SiO2 ,TiO2 and ITO films can be prepared by physical vapor deposition (PVD), chemical vapor deposition (CVD) or atomic layer deposition (ALD) and other processes; Ag films can be prepared by sol-gel method, CVD method, sputtering method and other processes.
本发明第二个方面提供了所述抗老化辐射冷却透明薄膜在制备汽车车窗、建筑窗户、手机屏幕等户外场所的应用。在太阳光照射下，精准的可见光与近红外透反射率切换性能使其兼具优异的采光与阻挡太阳光热量的能力，并且顶部辐射层的高发射率可以将窗户及室内热量通过大气透明窗口辐射到3K的宇宙而实现降温。The second aspect of the present invention provides the application of the anti-aging radiation cooling transparent film in the preparation of outdoor places such as automobile windows, building windows, and mobile phone screens. Under sunlight, the precise visible light and near-infrared transmittance and reflectivity switching performance enables it to have excellent lighting and the ability to block sunlight heat, and the high emissivity of the top radiation layer can radiate the window and indoor heat through the atmospheric transparent window to the 3K universe to achieve cooling.
本发明的抗老化辐射制冷透明薄膜可以添加在窗户制备过程中，并且辐射层与反射层可以分开加工，其中所述抗老化辐射制冷透明薄膜的辐射层远离窗户。在辐射层的外侧还可以设置中红外透明结构，此时辐射层可以不受影响地将热量以电磁波形式向外辐射。若辐射层最外层为中红外吸收材料，则其与中红外透明结构结合之后可进一步提升薄膜整体的辐射能力。The anti-aging radiation cooling transparent film of the present invention can be added in the process of preparing windows, and the radiation layer and the reflection layer can be processed separately, wherein the radiation layer of the anti-aging radiation cooling transparent film is far away from the window. A mid-infrared transparent structure can also be set on the outside of the radiation layer, and the radiation layer can radiate heat outward in the form of electromagnetic waves without being affected. If the outermost layer of the radiation layer is a mid-infrared absorbing material, it can further enhance the radiation capacity of the film as a whole after combining it with the mid-infrared transparent structure.
本发明第三个方面提供了一种辐射制冷制品，包括衬底材料以及位于所述衬底材料上的抗老化辐射制冷透明薄膜，其中所述抗老化辐射制冷透明薄膜的太阳光反射层与衬底材料接触。The third aspect of the present invention provides a radiation cooling product, comprising a substrate material and an anti-aging radiation cooling transparent film located on the substrate material, wherein the sunlight reflecting layer of the anti-aging radiation cooling transparent film is in contact with the substrate material.
优选地，所述的衬底材料包括硅酸盐玻璃、石英玻璃等无机玻璃、聚氯乙烯(PVC)、EVA(乙烯醇酸酯)等复合塑料玻璃。Preferably, the substrate material includes inorganic glass such as silicate glass and quartz glass, or composite plastic glass such as polyvinyl chloride (PVC) and EVA (ethylene vinyl acetate).
优选地，所述的辐射制冷制品中，在辐射层外侧还设有中红外透明或吸收结构，如SiO2玻璃、聚乙烯(PE)膜或聚甲基丙烯酸甲酯(PMMA)玻璃等。辐射制冷制品的结构可根据实际效果进行调整。Preferably, in the radiation cooling product, a mid-infrared transparent or absorbing structure is also provided outside the radiation layer, such asSiO2 glass, polyethylene (PE) film or polymethyl methacrylate (PMMA) glass, etc. The structure of the radiation cooling product can be adjusted according to the actual effect.
与现有技术相比，本发明至少具备以下有益效果：Compared with the prior art, the present invention has at least the following beneficial effects:
(1)本发明采用简单的薄膜结构得到兼顾采光与被动冷却性能的窗户，通过周期结构得到的反射层可以精准调节太阳光波段可见光透明度与近红外反射率的切换，实现了通过可见光与阻挡太阳光热量的调节，通过调节所选材料厚度及周期数可以进一步提升其转换波长及透过率与反射率，同时利用多层膜结构得到的中红外波段高发射率的辐射层，可以进一步将热量以电磁波的形式辐射到外太空从而实现降温。(1) The present invention adopts a simple thin film structure to obtain a window that has both lighting and passive cooling performance. The reflective layer obtained by the periodic structure can accurately adjust the switching of visible light transparency and near-infrared reflectivity in the sunlight band, thereby achieving the regulation of visible light and blocking sunlight heat. By adjusting the thickness of the selected material and the number of periods, its conversion wavelength and transmittance and reflectivity can be further improved. At the same time, the radiation layer with high emissivity in the mid-infrared band obtained by the multi-layer film structure can further radiate heat into outer space in the form of electromagnetic waves to achieve cooling.
(2)本发明的抗老化辐射制冷透明薄膜在可见光波段良好的透明度使其具有良好的采光能力，在近红外波段良好的反射率使窗户及内部空间避免被太阳光进一步加热，并且在中红外良好的发射率可以使其将内部热量向外发射，提高了窗户的散热能力。该薄膜使用抗老化性能良好的无机材料，可以避免长时间太阳照射导致的发黄与性能下降。(2) The good transparency of the anti-aging radiation cooling transparent film of the present invention in the visible light band enables it to have good lighting ability, the good reflectivity in the near infrared band prevents the window and the internal space from being further heated by sunlight, and the good emissivity in the mid-infrared band enables it to emit internal heat to the outside, thereby improving the heat dissipation capacity of the window. The film uses inorganic materials with good anti-aging performance, which can avoid yellowing and performance degradation caused by long-term sunlight exposure.
(3)本发明的反射层在设计过程中可以选择导电材料以提升其导电性能，在通电情况下被加热进而具有良好的除霜、除雾功能。本发明抗老化辐射制冷透明薄膜具有良好的采光、降温性能以及良好的抗老化能力，在汽车车窗、建筑窗户等领域具有良好的应用前景。(3) The reflective layer of the present invention can be designed with conductive materials to improve its conductivity, and when powered on, it is heated to provide good defrosting and defogging functions. The anti-aging radiation refrigeration transparent film of the present invention has good lighting and cooling properties and good anti-aging ability, and has good application prospects in the fields of automobile windows, building windows, etc.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例中的抗老化辐射制冷薄膜的结构简图与工作原理图，其中图1a为辐射制冷透明薄膜的结构简图，包括辐射层与反射层；图1b为薄膜的工作原理图。FIG1 is a simplified structural diagram and a working principle diagram of an anti-aging radiation cooling film in an embodiment, wherein FIG1a is a simplified structural diagram of a radiation cooling transparent film, including a radiation layer and a reflection layer; and FIG1b is a working principle diagram of the film.
图2a为实施例1中的周期材料非周期厚度的抗老化辐射制冷透明薄膜的结构示意图，图2b和图2c为该结构在太阳光波段及中红外波段的光谱仿真结果图。FIG2a is a schematic diagram of the structure of the anti-aging radiation cooling transparent film of periodic material and non-periodic thickness in Example 1, and FIG2b and FIG2c are diagrams of spectral simulation results of the structure in the solar band and the mid-infrared band.
图3a为实施例2中的布拉格反射镜周期结构抗老化辐射冷却透明薄膜的结构；图3b和图3c为该结构在太阳光波段及中红外波段的光谱仿真结果图。FIG3a is a structure of the anti-aging radiation cooling transparent film with a periodic structure of a Bragg reflector in Example 2; FIG3b and FIG3c are diagrams of spectrum simulation results of the structure in the sunlight band and the mid-infrared band.
图4a为实施例3中的无辐射层的布拉格反射镜抗老化辐射冷却透明薄膜的结构；图4b和图4c为该结构在太阳光波段及中红外波段的光谱仿真结果图。FIG4a is a structure of the anti-aging radiation cooling transparent film of the Bragg reflector without a radiation layer in Example 3; FIG4b and FIG4c are diagrams of spectral simulation results of the structure in the sunlight band and the mid-infrared band.
图5a为实施例4中的双曲超材料结构抗老化辐射制冷透明薄膜的结构示意图；图5b和图5c为该结构在太阳光波段及中红外波段的光谱仿真结果图。FIG5a is a schematic diagram of the structure of the hyperbolic metamaterial structure anti-aging radiation cooling transparent film in Example 4; FIG5b and FIG5c are diagrams of the spectrum simulation results of the structure in the sunlight band and the mid-infrared band.
图6a为实施例5中的具有除霜/除雾功能的抗老化辐射冷却透明薄膜的结构示意图；图6b为该结构在太阳光波段的光谱仿真结果图。FIG6a is a schematic diagram of the structure of the anti-aging radiation cooling transparent film with defrosting/defog functions in Example 5; FIG6b is a diagram of the spectrum simulation results of the structure in the sunlight band.
图7a和图7b为图3所示的结构分别在s偏振与p偏振入射条件下随入射光角度变化的平均光谱数据。FIG. 7 a and FIG. 7 b are average spectral data of the structure shown in FIG. 3 under s-polarized and p-polarized incident conditions respectively as the incident light angle changes.
具体实施方式DETAILED DESCRIPTION
下面将参照附图更详细地描述本发明公开的示例性实施例。虽然附图中显示了本发明公开的示例性实施例，然而应当理解，可以以各种形式实现本发明公开而不应被这里阐述的实施例所限制。相反，提供这些实施例是为了能够更透彻地理解本发明公开，并且能够将本发明公开的范围完整的传达给本领域的技术人员。The exemplary embodiments disclosed in the present invention will be described in more detail below with reference to the accompanying drawings. Although the exemplary embodiments disclosed in the present invention are shown in the accompanying drawings, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments described herein. On the contrary, these embodiments are provided to enable a more thorough understanding of the present invention and to fully convey the scope of the present invention to those skilled in the art.
本发明实施例中的抗老化辐射制冷透明薄膜，包括：(Ⅰ)太阳光反射层；或者(Ⅱ)太阳光反射层和位于所述太阳光反射层上的辐射层，所述抗老化辐射制冷透明薄膜在中红外波段的发射率大于30％，在近红外波段的反射率大于60％，在可见光波段的透明度大于30％。The anti-aging radiative cooling transparent film in the embodiment of the present invention comprises: (I) a sunlight reflecting layer; or (II) a sunlight reflecting layer and a radiation layer located on the sunlight reflecting layer. The anti-aging radiative cooling transparent film has an emissivity greater than 30% in the mid-infrared band, a reflectivity greater than 60% in the near-infrared band, and a transparency greater than 30% in the visible light band.
实施例中，太阳光反射层的结构为单层或者多层薄膜结构，单层薄膜的厚度为2nm～10μm，太阳光反射层整体厚度小于1000μm。太阳光反射层的材料选择如Ag、Al、ITO、SiO2、Si3N4、TiO2、Al2O3等常见材料，可进一步降低加工成本与工艺要求。In the embodiment, the structure of the sunlight reflection layer is a single-layer or multi-layer thin film structure, the thickness of the single-layer thin film is 2nm-10μm, and the overall thickness of the sunlight reflection layer is less than 1000μm. The material of the sunlight reflection layer is selected from common materials such as Ag, Al, ITO, SiO2,Si3N4 ,TiO2,Al2O3,etc. , which can further reduce processing costs and process requirements.
实施例中，太阳光反射层的结构为单层或者多层薄膜结构，辐射层单层薄膜厚度为0.01～500μm，辐射层整体厚度小于5000μm。辐射层选择SiO2、Si3N4、Al2O3等在可见光波段具有良好透明度且在中红外波段具有良好发射率的材料。In the embodiment, the structure of the sunlight reflection layer is a single layer or multi-layer thin film structure, the thickness of the single layer of the radiation layer is 0.01-500 μm, and the overall thickness of the radiation layer is less than 5000 μm. The radiation layer is made of materials such as SiO2 , Si3 N4 , Al2 O3 that have good transparency in the visible light band and good emissivity in the mid-infrared band.
进一步地，太阳光反射层的结构为周期结构，周期数>2。Furthermore, the structure of the sunlight reflecting layer is a periodic structure, and the number of periods is greater than 2.
进一步地，所述周期结构为布拉格反射镜结构(DBR)或双曲超材料结构(HMM)。Furthermore, the periodic structure is a Bragg reflector structure (DBR) or a hyperbolic metamaterial structure (HMM).
进一步地，布拉格反射镜结构每周期为Si3N4薄膜与SiO2薄膜组合，或者SiO2薄膜与TiO2薄膜组合，组合中每层薄膜的厚度为30～600nm。布拉格反射镜中每层薄膜的厚度等于入射光在相应层的1/4等效波长。Furthermore, each period of the Bragg reflector structure is a combination of Si3 N4 film and SiO2 film, or a combination of SiO2 film and TiO2 film, and the thickness of each film in the combination is 30 to 600 nm. The thickness of each film in the Bragg reflector is equal to 1/4 of the equivalent wavelength of the incident light in the corresponding layer.
进一步地，双曲超材料结构每周期为Ag薄膜与SiO2薄膜组合，或者Ag薄膜和ITO薄膜组合，组合中Ag薄膜的厚度为2～40nm，SiO2薄膜或者ITO薄膜的厚度为10～600nm。Furthermore, each period of the hyperbolic metamaterial structure is a combination of an Ag film and aSiO2 film, or a combination of an Ag film and an ITO film, in which the thickness of the Ag film is 2 to 40 nm, and the thickness of theSiO2 film or the ITO film is 10 to 600 nm.
实施例中的薄膜材料可根据加工条件与成本选择PVD或CVD进行加工，在平整基底表面逐层生长，厚度根据加工条件选择手动设置或者编程控制。The thin film material in the embodiment can be processed by PVD or CVD according to processing conditions and costs, and grow layer by layer on the flat substrate surface. The thickness can be manually set or programmatically controlled according to processing conditions.
本发明的一些实施例的抗老化辐射冷却透明薄膜的结构示意图如图1所示，薄膜由两部分组成，包括反射层与辐射层，反射层为周期结构排列的不同折射率材料，工作原理如图1b所示，薄膜在太阳光可见波段的高透过率使其具有良好的采光特性，近红外光波段的高反射率避免了窗户与室内空间被太阳光进一步加热，同时中红外良好的发射率使其可以将热量以电磁波的形式通过大气透明窗口发射至宇宙，从而实现被动冷却。The structural schematic diagram of the anti-aging radiation cooling transparent film of some embodiments of the present invention is shown in Figure 1. The film consists of two parts, including a reflective layer and a radiation layer. The reflective layer is a material with different refractive indices arranged in a periodic structure. The working principle is shown in Figure 1b. The high transmittance of the film in the visible band of sunlight gives it good lighting characteristics, and the high reflectivity in the near-infrared band prevents the windows and indoor spaces from being further heated by sunlight. At the same time, the good emissivity of the mid-infrared enables it to emit heat into the universe through the atmospheric transparent window in the form of electromagnetic waves, thereby achieving passive cooling.
实施例1Example 1
图2a展示了材料周期排列，厚度非周期分布的抗老化辐射冷却透明薄膜结构，其中材料为Si3N4与SiO2依次周期排列，厚度从上至下分别为88nm、235nm、199nm、124nm、196nm、252nm、175nm、127nm、75nm、133nm、185nm、137nm、341nm、134nm、275nm、177nm、203nm、146nm、186nm,、35nm、193nm、130nm、177nm、85nm、167nm、133nm、192nm、143nm、185nm、132nm、116nm。该结构在太阳光波段及中红外波段的光谱仿真结果如图2b和2c所示，该结构在可见光波段平均透过率83％，近红外波段平均反射率84.2％，说明该结构具有良好的可见光采光效果与阻挡太阳光加热的能力，并且可以实现两个波段范围内透明度与反射率的切换，同时中红外78％发射率使其具有良好的辐射制冷能力，该结构在温度40℃时可以功率为446W/m2的热量向外辐射热量，并且入射太阳光功率为900W/m2时仅透射124W/m2的近红外热量，进一步证明其被动冷却能力。Figure 2a shows an anti-aging radiation cooling transparent film structure with periodic arrangement of materials and non-periodic distribution of thickness, wherein the materials are Si3 N4 and SiO2 arranged periodically in sequence, and the thicknesses from top to bottom are 88nm, 235nm, 199nm, 124nm, 196nm, 252nm, 175nm, 127nm, 75nm, 133nm, 185nm, 137nm, 341nm, 134nm, 275nm, 177nm, 203nm, 146nm, 186nm, 35nm, 193nm, 130nm, 177nm, 85nm, 167nm, 133nm, 192nm, 143nm, 185nm, 132nm, and 116nm respectively. The spectral simulation results of the structure in the sunlight band and the mid-infrared band are shown in Figures 2b and 2c. The average transmittance of the structure in the visible light band is 83%, and the average reflectivity in the near-infrared band is 84.2%, indicating that the structure has good visible light lighting effect and the ability to block solar heating, and can achieve switching of transparency and reflectivity within the two bands. At the same time, the 78% emissivity of the mid-infrared gives it good radiation cooling ability. At a temperature of 40°C, the structure can radiate heat outward with a power of 446W/m2 , and when the incident sunlight power is 900W/m2, it only transmits 124W/m2 of near-infrared heat, further proving its passive cooling ability.
实施例2Example 2
图3a展示了布拉格反射镜周期结构抗老化辐射冷却透明薄膜的结构，反射层选择Si3N4与SiO2组成的布拉格反射镜周期结构，第一组DBR结构中Si3N4与SiO2的厚度分别为109nm与151nm，第二组DBR结构中Si3N4与SiO2的厚度分别为147nm与200nm，辐射层选择从上至下分别为125nm的Si3N4、210nm的SiO2与1700nm的Al2O3。该结构在太阳光波段及中红外波段的光谱仿真结果如图3b和3c所示，该结构在可见光波段平均透过率83％，近红外波段平均反射率91％，太阳光能量为900W/m2时仅透射120W/m2的近红外热量，同时中红外93％发射率使其在温度40℃时辐射功率高达490W/m2。Figure 3a shows the structure of the Bragg reflector periodic structure anti-aging radiation cooling transparent film. The reflective layer selects a Bragg reflector periodic structure composed of Si3 N4 and SiO2. The thicknesses of Si3 N4 and SiO2 in the first group of DBR structures are 109nm and 151nm respectively, and the thicknesses of Si3 N4 and SiO2 in the second group of DBR structures are 147nm and 200nm respectively. The radiation layer selects Si3 N4 of 125nm, SiO2 of 210nm and Al2 O3 of 1700nm from top to bottom. The spectral simulation results of the structure in the sunlight band and mid-infrared band are shown in Figures 3b and 3c. The structure has an average transmittance of 83% in the visible light band and an average reflectivity of 91% in the near-infrared band. When the sunlight energy is 900W/m2 , it only transmits 120W/m2 of near-infrared heat. At the same time, the 93% emissivity of the mid-infrared makes its radiation power as high as 490W/m2 at a temperature of 40℃.
实施例3Example 3
图4a展示了无辐射层的布拉格反射镜抗老化辐射冷却透明薄膜的结构，反射层选择Si3N4与SiO2组成的布拉格反射镜周期结构，第一组DBR结构中Si3N4与SiO2的厚度分别为109nm与151nm，第二组DBR结构中Si3N4与SiO2的厚度分别为147nm与200nm。该结构在太阳光波段及中红外波段的光谱仿真结果如图4b和4c所示，在可见光波段平均透过率92％，近红外波段平均反射率91％，太阳光功率为900W/m2时仅透射126W/m2的近红外热量，并且中红外78％的发射率使其在温度40℃时向外辐射热量的功率为439W/m2。Figure 4a shows the structure of the Bragg reflector anti-aging radiation cooling transparent film without radiation layer. The reflective layer is a Bragg reflector periodic structure composed of Si3 N4 and SiO2. The thickness of Si3 N4 and SiO2 in the first group of DBR structures are 109nm and 151nm respectively, and the thickness of Si3 N4 and SiO2 in the second group of DBR structures are 147nm and 200nm respectively. The spectral simulation results of the structure in the sunlight band and mid-infrared band are shown in Figures 4b and 4c. The average transmittance in the visible light band is 92%, the average reflectivity in the near-infrared band is 91%, and only 126W/m2 of near-infrared heat is transmitted when the solar power is 900W/m2. In addition, the 78% emissivity of the mid-infrared makes the power of heat radiated outward at a temperature of 40°C to be 439W/m2 .
实施例4Example 4
图5展示了双曲超材料周期结构抗老化辐射冷却透明薄膜的结构与光谱仿真结果。其中图5a展示了该薄膜的结构示意图，该结构中Ag与SiO2的厚度分别为14nm与1300nm，辐射层选择从上至下分别为230nm的Si3N4、485nm的SiO2与830nm的SiO2，该结构在太阳光波段及中红外波段的光谱仿真结果如图5b和5c所示，该结构在可见光波段平均透过率41％，近红外反射率93％，中红外发射率85％。Figure 5 shows the structure and spectrum simulation results of the hyperbolic metamaterial periodic structure anti-aging radiation cooling transparent film. Figure 5a shows the schematic diagram of the structure of the film. The thickness of Ag and SiO2 in the structure is 14nm and 1300nm respectively. The radiation layer is selected from top to bottom as 230nm Si3 N4 , 485nm SiO2 and 830nm SiO2. The spectrum simulation results of the structure in the sunlight band and mid-infrared band are shown in Figures 5b and 5c. The average transmittance of the structure in the visible light band is 41%, the near-infrared reflectivity is 93%, and the mid-infrared emissivity is 85%.
实施例5Example 5
图6a展示了具有除霜/除雾功能的抗老化辐射冷却透明薄膜的结构示意图。该薄膜选择导电性能良好的Ag和ITO组成的HMM结构，其中Ag的厚度为15nm，ITO的厚度为80nm，在太阳光波段的光谱仿真结果如图6b所示，可见光波段平均透过率40％，近红外反射率70％，良好的导电性能使其在电压作用下实现除霜/除雾效果。Figure 6a shows the schematic diagram of the structure of the anti-aging radiation cooling transparent film with defrosting/defogging function. The film selects the HMM structure composed of Ag and ITO with good conductivity, where the thickness of Ag is 15nm and the thickness of ITO is 80nm. The spectrum simulation results in the sunlight band are shown in Figure 6b. The average transmittance in the visible light band is 40%, and the near-infrared reflectivity is 70%. The good conductivity enables it to achieve defrosting/defogging effect under the action of voltage.
反射镜周期结构，第一组DBR结构中Si3N4与SiO2的厚度分别为109nm与151nm，第二组DBR结构中Si3N4与SiO2的厚度分别为147nm与200nmReflector periodic structure: the thickness of Si3 N4 and SiO2 in the first group of DBR structures is 109nm and 151nm respectively, and the thickness of Si3 N4 and SiO2 in the second group of DBR structures is 147nm and 200nm respectively.
图7展示了图3所示的结构分别在s偏振与p偏振入射条件下随入射光角度变化的平均光谱数据，包括平均可见光透过率、近红外平均反射率以及中红外平均吸收率。对于入射角<45°可见光，不同偏振薄膜的平均透过率大于50％，满足实际应用过程中的对采光的基本需求。Figure 7 shows the average spectral data of the structure shown in Figure 3 under s-polarized and p-polarized incident conditions, including average visible light transmittance, near-infrared average reflectance, and mid-infrared average absorptance. For visible light with an incident angle of <45°, the average transmittance of different polarizing films is greater than 50%, meeting the basic lighting requirements in practical applications.
以上仅为本申请的实施例而已，并不用于限制本申请。对于本领域技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原理之内所作的任何修改、等同替换、改进等，均应包含在本申请的权利要求范围之内。The above are only embodiments of the present application and are not intended to limit the present application. For those skilled in the art, the present application may have various changes and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included within the scope of the claims of the present application.
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