摘要
太阳能光伏用纳米减反射膜玻璃可提高太阳能电池的发电效率，缩短并网发电的成本回收期，提升其市场综合竞争力。在我国新能源战略规划的背景下，项目具有非常好的市场前景和应用价值。本项目用Sol-gel法制备出纳米SiO_2减反射镀膜溶液，在玻璃表面镀膜后，经热处理或钢化使膜层与玻璃基体牢固结合，获得透过率高、耐候性好、硬度高和耐划伤能力好的多孔纳米SiO_2膜，开发出太阳能电池响应波谱范围内具有高透过率的减反射膜玻璃。
本文首先采用正交试验法研究了醇硅摩尔比、水硅摩尔比、陈化时间、pH值等对酸催化、碱催化条件下合成了SiO_2溶胶的粘度、粒度及稳定性的影响，获得粒度可控的稳定溶胶。酸催化条件下制备的薄膜致密，硬度较高，耐划伤能力好，但增透效果欠佳。而碱催化条件下获得多孔结构的膜，可见光透过率可达98.22%，不过由于孔隙率很高，膜硬度低、耐磨性较差。
采用聚硅氧烷改性碱催化基础硅溶胶，缠绕或偶然分叉的线形链结构生长的聚硅氧烷被引入到体系中，填充到碱催化所得球形颗粒间的空隙中并形成相互粘连，导致溶胶粘度增加、稳定性提高。随着掺杂比例的提高，膜层孔隙率下降，折射率升高，而膜层表面变致密和光滑，膜耐候性、耐磨性及硬度显著提高。通过控制掺杂比例可实现薄膜折射率在1.23～1.42之间的连续可调。当聚硅氧烷掺杂比例从0％提升到16％时，膜的可见光透过率由97.81％降至94.24％，90天室外老化试验后的透过率衰减值从2.70％降至0.22％。掺杂5％的聚硅氧烷改性可兼顾碱性催化所得减反射膜的高透性与酸催化成膜性好、膜层牢固、硬度高等优势。
碱催化法获得的减反射膜硬度低、机械强度差，引入TiO_2、ZrO_2溶胶以及Al_2O_3溶液改性碱催化基础溶胶，这些氧化物填充到二氧化硅网络结构中起到较好的复合增强作用，膜的硬度、耐划伤能力等机械性能显著改善。TiO_2、ZrO_2、Al2O3掺杂比例的增加可提高膜的硬度，但添加量过多会引起膜的折射率升高、透过率下降，要选择适宜的掺加比例，才能在保证膜透过率的前提下改善其力学性能。
采用聚硅氧烷与纳米TiO_2溶胶复合改性碱性基础溶胶，制备出具有亲水性自清洁功能的减反射膜玻璃。引入纳米TiO_2改善了膜层表面状态，膜具有较好的亲水性，而且无定形纳米TiO_2作为纳米增强相提高了膜层硬度，与聚硅氧烷一起掺杂改性后膜的耐候性显著提高。该镀膜玻璃耐候性非常好，湿热试验后透过率衰减值仅为0.23％，膜层非常牢固，附着力为5B，铅笔硬度≥3H，而且镀膜玻璃合片制成组件成品的平均峰值功率较之采用未镀膜玻璃的组件提升了3.20％。
传统SiO_2膜易吸潮引起透过率衰减，本课题利用甲基三乙氧基硅烷（MTES）在酸催化条件下水解得到的溶胶对碱催化SiO_2溶胶改性处理，首次采用原位合成的方式向SiO_2网络中引入-Si-CH3疏水基团，使纳米SiO_2颗粒表面疏水化，获得单甲基改性的SiO_2溶胶，制备出具有疏水自清洁功能的减反射膜玻璃。红外光谱分析发现掺杂MTES后，膜的-OH基吸收峰减弱，而-CH3吸收峰增强，疏水甲基被成功的引入到膜层结构中，取代硅氧网络结构中的活性羟基，解决了膜层由于表面富含羟基而吸潮、吸水所导致的透过率衰减问题。MTES体积掺杂比例为40％时兼具高透过率、高疏水性能，膜层的可见光透过率达96.25%，接触角达到134.4°。
工业试验证明项目研发的纳米减反射溶液性能稳定、可靠，制备的太阳能光伏用纳米减反射膜玻璃透过率≥94.3％，膜层的附着力为5B级，铅笔硬度为4H，耐候性非常好，经客户试用证实合成组件的峰值功率提升达2.58％，为业内领先水平，具有非常好的市场前景和推广价值，可广泛的应用于太阳能光伏领域。
It can improve the generating efficiency of solar cells and shorten the cost recoveryperiod of grid-connected power generation using antireflective solar glass, and thecomprehensive competitiveness of the market is enhanced, so the project has very goodmarket prospect and application value under China's new energy strategy planningbackground. Nanometer SiO_2antireflection coating solution was prepared by Sol-gel method,porous SiO_2film was coated on the surface of the glass by suitable coating process, then heattreated or toughened, thus the coating and the glass substrate was firmly combined,antireflective glass for solar photovoltaic modules was successfully fabricated with hightransmittance in solar cell’s response spectral range, good weather resistance, high hardnessand good scratch resistant ability.
Factors that affecting synthesis of the acid-and base-catalyzed SiO_2sols, includingnH2O/nTEOS, nEtOH/nTEOS, aging time, pH value, et al., were studied systematically usingorthogonal test system firstly, effects on viscosity, particle size, stability of the sols wereanalyzed, and stable sols with controlled particle size were obtained. Film derived fromacid-catalyzed sol was tense and had good scratch resistant ability and high hardness, but theadded transmittance value was limited. Porous membrane with visible light transmittance ofup to98.22%was derived from base-catalyzed sol; however the film had poor wear resistanceand low hardness.
When the base-catalyzed sol doped with polysiloxane, macromolecules of entangledlinear or randomly branched chains formed in the acid catalyzed silica sols were introduced,long-chained polysiloxane was filled into the gaps between the spherical particles inbase-catalyzed sol and formed a mutual adhesion，which resulted in the increase of viscosityand improvement of system stability. With the doping ratio increased, porosity of films wasreduced and refractive index increased, the film became denser and smooth, resulting in thedesirable increase of the durability, abrasion resistance and hardness. Refractive index couldbe adjusted from1.23to1.42continuously by changing the doping ratio. When the dopingratio increased from0%to16%, the visible light transmittance of the film declined from97.81%to94.24%quickly, the transmittance attenuation after outdoor exposure for90daysreduced from2.70％to0.22%successfully, and the abrasive-resistance properties of thesilica films improved remarkably. Take all factors into consideration, the films derived frommodified base catalyzed sol with5vol%doping ratio exhibits high transmittance, good weather-resistance and high abrasion-resistance.
Antireflective film derived from the base catalyzed sol has low hardness and poormechanical strength. Mechanical properties of the films including hardness, scratch resistanceability had been significantly improved by introducing TiO_2sol, ZrO_2sol and Al_2O_3solutionto modify the base sol, because of the inorganic ceramic oxide filled to the silica networkstructure and acted as good composite reinforcement effect. The hardness of the film could beimproved continuously with the increasing TiO_2, ZrO_2, Al_2O_3doping ratio, but refractiveindex of the film increased, transmittance decreased when adding too much modifiers. Sochoosing suitable adding ratio is quite important, which can maintain the film mechanicalproperties and optical properties.
Polysiloxane and nano-TiO_2sol was used to modify the base-catalyzed sol, antireflectivesolar glass with hydrophilic self-cleaning function were prepared. The film’s hardness waspromoted the by amorphous TiO_2nanoparticles as nanometer reinforcing phase, and weatherresistance of the films derived from the modified sols was improved significantly. The filmshad excellent weather resistance, with degradation of transmittance after damp-heat test only0.23％. The adhesion of the film was5B, and pencil hardness of the film could be equal orhigher than3H. The average peak power output of solar module using antireflective glass wasimproved by3.20%than that of uncoated ones.
Due to the water absorbed from the surroundings, the transmittance of traditional silicacoatings declines with time. The base-catalyzed sol was modified by the sol derived frommethyl triethoxy silane (MTES) hydrolyzed under acid conditions. The-Si-CH3hydrophobicgroups were successfully introduced into the SiO_2network by means of in situ synthesis, somodified SiO_2sol was prepared with the surface of nano-SiO_2particles having hydrophobiceffect, and then antireflective solar glass with hydrophobic self-cleaning function wereprepared. Infrared spectroscopy analysis showed that hydrophobic methyl was successfullyintroduced to the film structure after doping MTES, with absorption peaks of-OH decreasedand absorption peak of-CH3enhanced, so the active hydroxyl silicone in the networkstructure had been replaced by hydrophobic methyl. Thus, the problem of transmissionattenuation of the films caused by moisture and water absorption was solved successfully.When the volume doping ratio of MTES was40%, the film had high transmittance of96.25%,and high hydrophobicity with contact angle of134.4°.
The nanometer antireflective solutions were stable and reliable researched in this project.Durable antireflective glass for solar photovoltaic modules was prepared with transmittance≥94.3%, coating adhesion to5B level and pencil hardness of4H. It was proved by the customer that the peak power of modules using the products was improved by more than2.58%. As theindustry leading level, it has a very good market prospect and promotion value, and can bewidely used in the field of solar photovoltaic.
引文
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