CN112311323B - 一种多晶硅平板型荧光太阳集光器的制备方法及其应用 - Google Patents
一种多晶硅平板型荧光太阳集光器的制备方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种基于核壳量子点掺杂PHPS/PMMA的多晶硅平板型荧光太阳集光器的制备方法,特点是包括发光中心材料铝铟硫/硒化锌核壳量子点制备的步骤;将全氢聚硅氮烷、聚甲基丙烯酸甲酯混合后不断搅拌,混合均匀,得到前驱液A,将AIS/ZnSe核壳量子溶解于二甲苯中,搅拌混合得到前驱液B;然后将前驱液A和前驱液B按体积比10:1的比例在旋涡混合器上混合振荡后超声处理,置于真空干燥箱中抽气后装入模具中,采用真空加热的方法进行紫外光固化,固化脱模后,再经过切割、抛光工艺,即得到基于核壳量子点掺杂PHPS/PMMA的多晶硅平板型荧光太阳集光器,优点是光子输运效率高且集光效率高。
Description
技术领域
本发明涉及一种平板型荧光太阳集光器,尤其是涉及一种基于核壳量子点掺杂PHPS/PMMA的多晶硅平板型荧光太阳集光器的制备方法。
背景技术
多晶硅太阳电池组件是通过浇铸、定向凝固的方法制成多晶硅的晶锭,再经过切割、打磨等工艺制成多晶硅片,进一步经过清洗、扩散、沉积减反膜、丝印电极和烧结等工序制成的。与单晶硅太阳能电池组件相比,多晶硅太阳能电池的制备工艺简单,成品率高,生产环节中无污染,能耗和成本低;与非晶硅薄膜太阳能电池相比,多晶硅太阳能电池的使用寿命更长且光电转换效率高。随着可供单晶硅太阳能电池生产的头尾料越来越少以及多晶硅太阳能电池的生产工艺不断改进,多晶硅太阳能电池逐渐占据了太阳能电池市场的主要份额。作为一种主要的太阳能电池产品,如何提高多晶硅太阳能电池的单位成本发电量,是限制当前多晶硅太阳能电池发展的技术瓶颈之一。平板型荧光太阳集光器可以有效提高多晶硅太阳能电池板单位面积的发电量,与基于菲涅尔聚光原理的传统聚光光伏技术相比,平板型荧光太阳集光器采用面聚焦,因此无需实时逐日系统,也不存在明显的热效应,受到工业界和科学研究同行的广泛关注。一般说来,平板型荧光太阳集光器的核心由两部分组成,即发光中心材料和光子输运基质材料。
一方面,目前已报道的平板型荧光太阳集光器中的发光中心材料普遍采用单一种类的半导体量子点或有机染料分子。由于部分量子点和有机染料分子的稳定性较差,在长时间AM1.5光照条件下易分解(如钙钛矿量子点等)、部分量子点的光致发光量子产率低,集光效率低下(如碳量子点等)、部分量子点和有机染料分子毒性较强,制备工艺复杂(如硫化镉、硫化铅等量子点)。现有的以量子点和有机染料分子作为发光中心材料的平板型集光器面临着集光效率低、工作稳定性差等技术难题。更为严重的是,由于半导体量子点独特的能带结构以及有机染料分子特定的类原子能级结构,单一发光中心材料的吸收峰与发射峰的波长接近。对平板型荧光太阳集光器而言,小的斯托克斯位移意味着器件光子输运过程中的重吸收问题严重,最终将导致平板型荧光太阳集光器的光子输运效率低、集光效率低等问题,这严重限制了平板型集光光伏器件的发展和总体集光性能的提升。
另一方面,除了发光中心材料,平板型荧光太阳集光器中的光子输运基质材料也极大的影响了器件集光效率。目前已报道的PMMA、PDMS、OSTE、PE、PET等聚合物等光波导材料的折射率普遍偏低。根据全反射定律,光子输运基质材料的折射率越低,其光子的逃逸率越高,最终导致器件的集光效率低下。另一方面,PMMA、PDMS、OSTE、PE、PET等聚合物的可见光透光性普遍低于90%,硬度普遍低于6H。单一聚合物基质中的气泡、颗粒物团簇以及悬挂键是常见的非辐射复合中心,导致光子转换过程中辐射复合效率相对较低,荧光寿命短,光子的输运效率低,最终导致器件的集光效率不高。
发明内容
本发明所要解决的技术问题是提供一种发光中心材料与光子输运基质材料兼容性好,且集光效率大幅提升的基于核壳量子点掺杂PHPS/PMMA的多晶硅平板型荧光太阳集光器的制备方法,本发明解决上述技术问题所采用的技术方案为:一种基于核壳量子点掺杂PHPS/PMMA的多晶硅平板型荧光太阳集光器的制备方法,包括以下步骤:
(1)发光中心材料银铟硫(AIS)/硒化锌(ZnSe)核壳量子点的制备
A.将0.16g N-乙酰-L-半胱氨酸(C5H9NO3S)作为保护剂、0.16g谷胱甘肽(C10H17N3O6S)作为稳定剂、0.20-0.80mL硝酸银(AgNO3)溶液、0.04-0.15mL硝酸铟(In(NO3)3)溶液溶于80mL去离子水中,不断搅拌直至混合均匀,在上述混合溶液中,逐滴加入稀释后的氢氧化钠(NaOH)溶液,调节混合溶液的pH值至7-9后置于三颈圆底烧瓶内,通入氮气保护气体,在室温下,将0.5-3.0mL硫化钠(Na2S)溶液快速注入混合液中,搅拌10-30min并采用油浴加热至80-120℃,并保持1-3h;
B.在氮气气氛保护下,将0.1974g硒(Se)粉末,0.25g硼氢化钠(NaBH4)固体粉末和0.8784乙酰丙酮锌(C10H14O4Zn)固体粉末溶解在10ml的去离子水中,不断搅拌,混合均匀,获得硒化锌(ZnSe)前驱液;
C.最后将10mL硒化锌前驱液快速注入步骤A制备得到的混合液中,搅拌10-30min并采用油浴加热至120℃,并保持1h,将溶液冷却至室温,加入NaOH溶液和丙酮溶液进行沉淀,反复离心和清洗,并用去离子水洗涤数次,在室温下干燥后得到AIS/ZnSe核壳量子点;
(2)AIS/ZnSe核壳量子点掺杂PHPS/PMMA集光层的制备
将全氢聚硅氮烷(PHPS)、聚甲基丙烯酸甲酯(PMMA)按质量比(0.2-0.8):0.2的比例混合后不断搅拌,混合均匀,得到前驱液A;随后将步骤(1)制备的AIS/ZnSe核壳量子点按质量体积比溶1mg:10mL的比例溶解于二甲苯(C8H10)中,不断搅拌,混合均匀,得到前驱液B;然后将前驱液A和前驱液B按体积比10:1的比例在旋涡混合器上混合振荡1-3min后超声处理2-10min,置于真空干燥箱中抽气150-200min后,装入模具中,采用真空加热的方法进行紫外光固化,加热温度为200-400℃,固化脱模后,再经过切割、抛光工艺,即得到基于核壳量子点掺杂PHPS/PMMA的多晶硅平板型荧光太阳集光器。
上述基于核壳量子点掺杂PHPS/PMMA的多晶硅平板型荧光太阳集光器在制备多晶硅平板型集光光伏发电装置方面的应用。
上述多晶硅平板型集光光伏发电装置的制备方法,包括以下步骤:采用超白光伏玻璃作为基板与底部保护层;在超白光伏玻璃表面淀积400nm-1um金属层作为光子反射层;将权利要求1所述的多晶硅平板型荧光太阳集光器固定在金属层上表面;在多晶硅平板型荧光太阳集光器的上表面设置顶部减反层;将长条状多晶硅太阳能电池板采用紫外固化胶固定在多晶硅平板型荧光太阳集光器、金属层和光伏玻璃的两端,用导线将四周的太阳能电池板串联起来,最终得到基于AIS/ZnSe核壳量子点的多晶硅平板型集光光伏发电装置。
所述的金属层为金、银和铜金属中的一种或几种;所述的长条状多晶硅太阳能电池板的尺寸为长15.6厘米,宽0.1至1.0厘米。
工作原理:当太阳光入射至器件表面时,顶部减反层的结构设计可有效减少太阳光的反射,从而使得更多的太阳光子进入器件内部集光层。平板型荧光太阳集光器中内部集光层的发光中心材料是AIS/ZnSe核壳量子点,其吸收太阳光后,经过光致发光过程,产生中心波长在730nm的特征荧光发射。内部集光层的基质材料是PHPS/PMMA,其折射率远远大于空气的折射率。当发光中心材料发出特征荧光后,由于传播过程中荧光的全反射过程,将大部分光子限制在平板型荧光太阳集光器内,部分发射的光子从下层透射后,由于金属薄膜的反射作用,将重新回到多晶硅平板型荧光太阳集光器内。经过多晶硅平板型荧光太阳集光器内部的多个全发射过程后,最终达到商用多晶硅太阳能电池板的表面,从而达到集光和提高单位面积多晶硅太阳能电池板发电量的目的。
与现有技术相比,本发明的优点在于
(1)基于核壳量子点掺杂的PHPS/PMMA的多晶硅平板型荧光太阳集光器采用AIS/ZnSe核壳量子点作为发光中心,一方面,由于经过PMMA改性后的PHPS的化学修饰等表面钝化作用,减少了量子点表面的悬挂键等非辐射复合中心的密度,因此大幅提升了传统单一量子点的光致发光转换效率;另一方面AIS/ZnSe核壳量子点的特征吸收峰与发射峰之间存在大的斯托克斯位移(>200nm),大大高于已报道的用于荧光太阳集光器的单一种类量子点(如碳量子点,钙钛矿量子点,硫化铅量子点等,其斯托克斯位移普遍小于20nm),更大的斯托克斯位移,可有效避免传统单一量子点的光谱重吸收问题,从而大幅提升了平板型荧光太阳集光器的光子输运效率,最终获得高的集光效率。
(2)AIS/ZnSe核壳量子点与聚合物基质(PHPS/PMMA)的互溶度高,透光度好。相比于已报道的荧光太阳集光器光子输运基质材料PMMA、PDMS、OSTE、PE、PET等,经过PMMA改性后的PHPS用于荧光太阳集光器的基质材料,其透光度>95%,且硬度高(可达9H)、隔声性能好(1000Hz以下大于50dB)、耐腐蚀、抗氧化、热稳定性好。
(3)AIS/ZnSe核壳量子点与聚合物基质(PHPS/PMMA)两者之间存在协同增强作用。PHPS/PMMA可有效钝化核壳量子点表面的悬挂键等非辐射复合中心,从而提高量子点发光的量子产率。针对AIS/ZnSe核壳量子点作为发光中心材料,相比于已报道的荧光太阳集光器光子输运基质材料PMMA等,PHPS/PMMA基质中的核壳量子点的荧光寿命更长(图3)、紫外灯照射下发光稳定性好(图4,图5)。
(4)基于AIS/ZnSe核壳量子点掺杂的PHPS/PMMA的光伏发电装置(图2)可有效减少入射光子表面反射损耗以及平板型光波导内传输损耗,从而显著提高平板型集光多晶硅光伏器件光学收集效率(经积分球测试后计算,6.52%)以及商用多晶硅太阳能电池的光电转换效率。
(5)光谱匹配程度是影响太阳能电池发电效率的重要因素之一,同时也会影响到功率测试结果的精准度。商用多晶硅电池的最佳光谱响应波段峰值在600-900nm。太阳能电池的光谱响应是指当某一波长的光照射在电池表面上时,每一光子平均所能产生的载流子数,反映了太阳能电池将不同波段入射光的光能转换成电能的能力。本发明设计的平板型集光器件中的发光中心材料AIS/ZnSe核壳量子点的特征荧光发光中心峰位在730nm。AIS/ZnSe核壳量子点掺杂的PHPS/PMMA与多晶硅太阳能电池的匹配度高(图1)。
综上所述,本发明一种基于核壳量子点掺杂的PHPS/PMMA的多晶硅平板型荧光太阳集光器的制备方法,其制备的AIS/ZnSe核壳量子点(发光中心材料)发光斯托克斯位移大;经PMMA修饰的PHPS(光子输运基质材料)的硬度高,透光性好,声子能量低;进一步,PMMA修饰的PHPS可有效钝化核壳量子点表面的悬挂键等非辐射复合中心,两者之间的协同作用,使得集光效率大幅提升;更进一步,730nm处的特征发光与多晶硅太阳能电池的最佳响应光谱的匹配度高,使进一步制备的平板型集光光伏发电装置具有高的单位成本发电量。基于AIS/ZnSe核壳量子点掺杂的PHPS/PMMA的光伏发电装置可有效减少入射光子表面反射损耗以及平板型光波导内传输损耗,从而显著提高在弱光照条件下的平板型集光多晶硅光伏器件光学收集效率以及商用多晶硅太阳能电池的光电转换效率。
附图说明
图1为AM1.5标准太阳光谱,AIS/ZnSe核壳量子点光致发光谱以及商用多晶硅太阳能电池光谱响应谱;
图2为本发明基于AIS/ZnSe核壳量子点的多晶硅平板型集光光伏发电装置结构示意图;
图3为AIS/ZnSe核壳量子点在不同光子输运基质材料中的荧光寿命对比图;
图4为AIS/ZnSe核壳量子点在PHPS/PMMA中的发光强度稳定性示意图;
图5为AIS/ZnSe核壳量子点在PHPS/PMMA中的发光峰位稳定性示意图。
具体实施方式
以下结合附图实施例对本发明作进一步详细描述。
具体实施例一
一种基于核壳量子点掺杂PHPS/PMMA的多晶硅平板型荧光太阳集光器的制备方法,包括以下步骤:
(1)发光中心材料银铟硫(AIS)/硒化锌(ZnSe)核壳量子点的制备
A.将0.16g N-乙酰-L-半胱氨酸(C5H9NO3S)作为保护剂、0.16g谷胱甘肽(C10H17N3O6S)作为稳定剂、0.20-0.80mL硝酸银(AgNO3)溶液、0.04-0.15mL硝酸铟(In(NO3)3)溶液溶于80mL去离子水中,不断搅拌直至混合均匀,在上述混合溶液中,逐滴加入稀释后的氢氧化钠(NaOH)溶液,调节混合溶液的pH值至7-9后置于三颈圆底烧瓶内,通入氮气保护气体,在室温下,将0.5-3.0mL硫化钠(Na2S)溶液快速注入混合液中,搅拌10-30min并采用油浴加热至80-120℃,并保持1-3h;
B.在氮气气氛保护下,将0.1974g硒(Se)粉末,0.25g硼氢化钠(NaBH4)固体粉末和0.8784乙酰丙酮锌(C10H14O4Zn)固体粉末溶解在10ml的去离子水中,不断搅拌,混合均匀,获得硒化锌(ZnSe)前驱液;
C.最后将10mL硒化锌前驱液快速注入步骤A制备得到的混合液中,搅拌10-30min并采用油浴加热至120℃,并保持1h,将溶液冷却至室温,加入NaOH溶液和丙酮溶液进行沉淀,反复离心和清洗,并用去离子水洗涤数次,在室温下干燥后得到AIS/ZnSe核壳量子点;由图1可知,AIS/ZnSe核壳量子点光致发光谱的中心波长,完全覆盖多晶硅太阳能电池的最佳光谱响应;
(2)AIS/ZnSe核壳量子点掺杂PHPS/PMMA集光层的制备
将全氢聚硅氮烷(PHPS)、聚甲基丙烯酸甲酯(PMMA)按质量比(0.2-0.8):0.2的比例混合后不断搅拌,混合均匀,得到前驱液A;随后将步骤(1)制备的1mg AIS/ZnSe核壳量子点溶解于10ml二甲苯(C8H10)中,不断搅拌,混合均匀,得到前驱液B;然后将前驱液A和前驱液B按体积比10:1的比例在旋涡混合器上混合振荡1-3min后超声处理2-10min,置于真空干燥箱中抽气150-200min后,装入模具中,采用真空加热的方法进行紫外光固化,加热温度为200-400℃,固化脱模后,再经过切割、抛光工艺,即得到基于核壳量子点掺杂PHPS/PMMA的多晶硅平板型荧光太阳集光器。
具体实施例二
多晶硅平板型集光光伏发电装置的制备方法,如图2所示,包括以下步骤:采用商用超白光伏玻璃作为基板与底部保护层;采用电子束蒸发、热蒸发或者磁控溅射工艺在超白光伏玻璃表面淀积400nm-1um金属层,作为光子反射层,防止太阳光子从底部逃逸;将具体实施例一所述的多晶硅平板型荧光太阳集光器固定在金属层上表面;在多晶硅平板型荧光太阳集光器的上表面采用光刻技术结合等离子体刻蚀技术、或直接采用纳米压印技术设计顶部减反层,提高太阳光子入射效率;采用激光划片机将多晶硅太阳能电池板切割成长条状(如15.6cm×0.5cm),采用紫外固化胶固定在多晶硅平板型荧光太阳集光器、金属层和光伏玻璃的两端,用导线将四周的太阳能电池板串联起来,最终得到基于AIS/ZnSe核壳量子点的多晶硅平板型集光光伏发电装置。
上述金属层为金、银和铜金属中的一种或几种;长条状多晶硅太阳能电池板的尺寸为长15.6厘米,宽0.5厘米。
基于AIS/ZnSe核壳量子点掺杂的PHPS/PMMA的光伏发电装置(图2)可有效减少入射光子表面反射损耗以及平板型光波导内传输损耗,从而显著提高平板型集光多晶硅光伏器件光学收集效率,经积分球测试后计算,平板型集光多晶硅光伏器件集光效率可达6.52%。
对比试验
1、不同发光中心材料对比
表1
有上述表1可知,基于核壳量子点掺杂的PHPS/PMMA的多晶硅平板型荧光太阳集光器采用AIS/ZnSe核壳量子点作为发光中心,一方面,由于PHPS的化学修饰等表面钝化作用,大幅提升了传统单一量子点的光致发光转换效率;另一方面AIS/ZnSe核壳量子点的特征吸收峰与发射峰之间存在大的斯托克斯位移(>200nm),大大高于已报道的用于荧光太阳集光器的单一种类量子点(如碳量子点,钙钛矿量子点,硫化铅量子点等,其斯托克斯位移普遍小于20nm),更大的斯托克斯位移,可有效避免传统单一量子点的光谱重吸收问题,从而大幅提升了平板型荧光太阳集光器的光子输运效率,最终获得高的集光效率。
图3为AIS/ZnSe核壳量子点在不同光子输运基质材料中的荧光寿命;AIS/ZnSe核壳量子点与聚合物基质(PHPS/PMMA)两者之间存在协同增强作用。针对AIS/ZnSe核壳量子点作为发光中心材料,相比于已报道的荧光太阳集光器光子输运基质材料PMMA等,由图3可知,PHPS/PMMA基质中的核壳量子点的荧光寿命更长。
图4为AIS/ZnSe核壳量子点在PHPS/PMMA中的发光强度稳定性示意图。经过标准AM1.5太阳光照10天后,AIS/ZnSe核壳量子点在PHPS/PMMA中的发光强度仍然能够保持98%以上,这大大优于目前已报道的OSTE中的钙钛矿量子点的发光强度稳定性。
图5为AIS/ZnSe核壳量子点在PHPS/PMMA中的发光峰位稳定性示意图。经过标准AM1.5太阳光照10天后,AIS/ZnSe核壳量子点在PHPS/PMMA中的发光峰位基本保持不变,这大大优于目前已报道的OSTE中的钙钛矿量子点的发光峰位稳定性。
综上所述,AIS/ZnSe核壳量子点与聚合物基质(PHPS/PMMA)的互溶度高,透光度好。相比于已报道的荧光太阳集光器光子输运基质材料PMMA、PDMS等,经过PMMA改性后的PHPS用于荧光太阳集光器的基质材料,其透光度>95%,且硬度高(可达9H)、隔声性能好(1000Hz以下大于50dB)、耐腐蚀、抗氧化、热稳定性好。
上述说明并非对本发明的限制,本发明也并不限于上述举例。本技术领域的普通技术人员在本发明的实质范围内,做出的变化、改型、添加或替换,也应属于本发明的保护范围。
Claims (3)
1.一种多晶硅平板型荧光太阳集光器的制备方法,其特征在于包括以下步骤:
(1)发光中心材料银铟硫/硒化锌核壳量子点的制备
A.将 0.16g N-乙酰-L-半胱氨酸、0.16g谷胱甘肽、0.20-0.80mL 硝酸银溶液、0.04-0.15mL 硝酸铟溶液溶于80mL去离子水中,不断搅拌直至混合均匀,在上述混合溶液中,逐滴加入稀释后的氢氧化钠溶液,调节混合溶液的pH值至7-9后置于三颈圆底烧瓶内,通入氮气保护气体,在室温下,将0.5-3.0mL 硫化钠溶液快速注入混合液中,搅拌10-30 min并采用油浴加热至80-120℃,并保持1-3 h;
B.在氮气气氛保护下,将0.1974g硒粉末,0.25g硼氢化钠固体粉末和0.8784乙酰丙酮锌固体粉末溶解在10ml的去离子水中,不断搅拌,混合均匀,获得硒化锌前驱液;
C.最后将10mL硒化锌前驱液快速注入步骤A制备得到的混合液中,搅拌10-30 min并采用油浴加热至120℃,并保持1 h,将溶液冷却至室温,加入NaOH溶液和丙酮溶液进行沉淀,反复离心和清洗,并用去离子水洗涤数次,在室温下干燥后得到AIS/ZnSe核壳量子点;
(2) AIS/ZnSe核壳量子点掺杂PHPS/PMMA集光层的制备
将全氢聚硅氮烷、聚甲基丙烯酸甲酯按质量比(0.2-0.8):0.2的比例混合后不断搅拌,混合均匀,得到前驱液A;将步骤(1)制备的AIS/ZnSe核壳量子点按质量体积比溶1mg:10mL的比例溶解于二甲苯中,不断搅拌,混合均匀,得到前驱液B;然后将前驱液A和前驱液B按体积比10:1的比例在旋涡混合器上混合振荡1-3min后超声处理2-10min,置于真空干燥箱中抽气150-200min后,装入模具中,采用真空加热的方法进行紫外光固化,加热温度为200-400℃,固化脱模后,再经过切割、抛光工艺,即得到基于核壳量子点掺杂PHPS/PMMA的多晶硅平板型荧光太阳集光器。
2.一种多晶硅平板型集光光伏发电装置的制备方法,其包括利用权利要求1所述的制备方法制得的多晶硅平板型荧光太阳集光器,其特征在于还包括以下步骤:采用超白光伏玻璃作为基板与底部保护层;在超白光伏玻璃表面淀积400nm-1um金属层作为光子反射层;将所述的多晶硅平板型荧光太阳集光器固定在金属层上表面;在所述的多晶硅平板型荧光太阳集光器的上表面设置顶部减反层;将长条状多晶硅太阳能电池板采用紫外固化胶固定在多晶硅平板型荧光太阳集光器、金属层和光伏玻璃的两端,用导线将四周的太阳能电池板串联起来,最终得到基于AIS/ZnSe核壳量子点的多晶硅平板型集光光伏发电装置。
3.根据权利要求2所述的一种多晶硅平板型集光光伏发电装置的制备方法,其特征在于:所述的金属层为金、银和铜金属中的一种或几种;所述的长条状多晶硅太阳能电池板的尺寸为长15.6厘米,宽0.1-1.0厘米。
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