CN110896111B - 一种基于量子点-磷光有机分子杂化材料的太阳能聚光板 - Google Patents
一种基于量子点-磷光有机分子杂化材料的太阳能聚光板 Download PDFInfo
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Abstract
本发明涉及一种基于量子点‑磷光有机分子杂化材料的高效太阳能聚光板。该太阳能聚光板主要由量子点作为光吸收材料，磷光有机分子作为光发射材料，聚合物作为光波导介质。利用量子点较大的消光系数高效吸光，并将能量转移到磷光有机分子，并通过其较大的光谱斯托克斯位移有效减小自吸收损失，最终通过聚合物光波导到侧面的太阳能电池实现光电转换。所述的磷光有机分子具有高效的磷光发射效率。作为优选方案，聚合物选用聚乙烯吡咯烷酮(PVP)，量子点选用碲化镉(CdTe)，可与磷光有机分子Pt‑tetraphenyltetrabenzoporphyrin(Pt(tpbp))实现最优化的光谱匹配，最终获得高达9％的外部量子效率。
Description
技术领域
本发明涉及一种基于量子点-磷光有机分子杂化材料的高效太阳能聚光板。
背景技术
太阳能聚光板(LSCs)是一种吸收太阳光并利用全反射效应聚集荧光，进而耦合到光伏电池，最终产生电力的荧光器件。相比传统太阳能模块，LSCs具有更低的光伏成本，以及实现(半)透明智能窗户的潜力。如果其聚光效率足够高，则一块LSC加上边缘处的少量太阳能电池在功能上等同于一整块大面积的太阳能电池。由于LSC的主体部分由廉价的有机玻璃材料加少量的发光材料组成，这一技术将有可能显著降低光伏产能的成本，对光伏产能领域带来革命性的改变。
尽管具有上述潜在优点，但目前报道的LSC研究都没有实现商业化，一个最主要的原因就是LSC效率都不够高。LSC的光学效率(外部量子效率，ηs,ext)是指LSC将入射到板上的太阳光子汇聚到板的边缘的量子效率，它主要由发光材料对太阳光的吸收效率(ηs,abs)、发光材料的荧光量子效率(ΦPL)和荧光光子波导传输效率(Φwg)决定。传统的发光材料，比如有机染料分子，基本上无法同时满足以上三个要素。具有高荧光效率的分子通常吸收在紫外和可见光区，无法有效地吸收太阳光中的近红外和红外光子(ηs,abs较低)；而近红外的染料分子(ηs,abs较高)则几乎不发荧光(ΦPL较低)。另外，大部分有机染料分子的消光系数较小、且吸收光谱和发射光谱之间存在较大的重叠(斯托克斯位移不够大)，导致发出的荧光光子在波导过程中由于重吸收损失掉(Φwg较低)。我们注意到，胶体量子点具备较高的消光系数、较宽的可调谐吸收和发射光谱以及出色的光稳定性和溶液法加工优点，目前已广泛应用于LSC研究中。但不可避免地，量子点荧光材料仍然具有一定的自吸收和较低的量子效率，促使其LSCs存在效率提升瓶颈。本发明提出，利用近红外量子点高效吸收太阳光子，并将能量通过Dexter能量转移机制高效转移给附近的磷光有机分子，有效地克服了量子点的自吸收损失；最后通过高效的磷光发射被LSC边缘的太阳能电池收集转化为电力。
我们设计并合成了碲化镉(CdTe)近红外量子点，并与能级匹配的磷光有机分子Pt-tetraphenyltetrabenzoporphyrin(Pt(tpbp))构建了异质结纳米颗粒，通过计算得出，基于该体系的LSC可以实现～36％的内部量子效率和～9％的外部量子效率。该发明为今后发展基于量子点的高性能LSC提供了基础，为最终实现商业化奠定了前提。
发明内容
本发明的目的在于，提供一种基于量子点-磷光有机分子杂化材料的高效太阳能聚光板，以解决太阳能聚光板效率偏低的技术问题。
所述的太阳能聚光板由量子点、磷光有机分子和聚合物混合而成的波导层组成。
所述的量子点组成可以为：元素周期表中第二副族的锌、镉或汞与第六主族的硫、硒或碲元素组成的化合物；磷化铟、硒化铅、碲化铅；以及三卤素钙钛矿量子点(具有ABX3结构，其中A＝Cs，CH3NH3，或CH(NH2)2；B＝Pb或Sn；X＝Cl,Br和I中的一种或两种以上)；也可以是铜或锰元素掺杂(掺杂量在1-20％，元素摩尔比)的量子点。
所述的磷光有机分子为Platinum octaethylporphyrin(Pt(oep))、Pt-tetraphenyltetrabenzoporphyrin(Pt(tpbp))、Bis[2-(2-pyridinyl-N)phenyl-C](acetylacetonato)iridium(III)(Ir(ppy)2(acac))及其衍生物。
所述的聚合物为聚乙烯吡咯烷酮(PVP)、聚乙烯醇(PVA)或聚甲基丙烯酸甲酯(PMMA)。
所述的高效太阳能聚光板采用本领域公知的方法制备得到。优选的量子点为碲化镉(CdTe)量子点；优选的磷光有机分子为Pt(tpbp)；优选的制备方法为刮刀流延法，该方案制备简单，并在今后有望实现加工成本低廉的太阳能聚光板制备。
为了验证上述太阳能聚光板是否真正实现了高效的光学效率，本发明采用的验证技术方案为：
利用稳态吸收和荧光光谱，确定碲化镉量子点与Pt(tpbp)的基本光吸收、发射特性和荧光量子效率。
基于上述光谱数据，建立模型计算基于该发明制备的LSC的光学效率。
附图说明
图1,太阳能聚光板示意图。
图2，(a)CdTe量子点的紫外-可见吸收光谱和荧光光谱；(b)Pt(tpbp)分子的紫外-可见吸收光谱和荧光光谱。
图3，(a)不同浓度的CdTe量子点的吸光度；(b)不同浓度的CdTe量子点对太阳光的吸收效率。
图4，(a)不同尺寸的太阳能聚光板在不同太阳光吸收效率下的内部量子效率；(b)不同尺寸的太阳能聚光板在不同太阳光吸收效率下的外部量子效率。
具体实施方式
本发明通过实施例和附图做进一步的说明。
实施例
本实施例所述一种基于量子点-磷光有机分子杂化材料的高效太阳能聚光板，其制备方法包括以下步骤：
0.1μmol CdTe量子点的氯仿溶液(10mL)与2mg的Pt(tpbp)分子混合放置于超声机中超声10分钟，在快速搅拌的前提下，向其快速注入5ml的去离子水，获得CdTe-Pt(tpbp)纳米颗粒。紧接着，将上述纳米颗粒与0.6g的聚乙烯吡咯烷酮混合搅拌10小时，最后利用刮刀流延法将其均匀涂布在玻璃基底上，静置直至溶剂完全挥发，形成太阳能聚光板，如图1所示。
我们制备获得的太阳能聚光板是否能实现高效的光学效率，需利用光学检测手段与理论计算结合予以验证，验证检测主要从以下两个方面进行：
(1)CdTe量子点和Pt(tpbp)分子的吸收、荧光光谱。
利用稳态吸收和荧光光谱检测手段，对CdTe量子点和Pt(tpbp)分子的吸收和荧光特性进行测试(样品浓度均为0.01mmol/L，氯仿溶液)，其中，紫外-可见稳态吸收光谱采用安捷伦carry 5000仪器获得；荧光光谱的激发波长为400nm，采用安捷伦Cary Eclipse荧光分光光度计获得，如图2所示。
(2)计算基于CdTe-Pt(tpbp)体系的聚光板的光学效率。
首先通过配置不同浓度(浓度间隔为0.01光学密度(OD))的CdTe量子点(图3a)计算其对太阳光的吸收效率(ηs,abs，图3b，测定方法参见Nature Photonics,2018,12,105.)；CdTe量子点到Pt(tpbp)分子的Dexter能量转移效率为100％，那么基于图2的吸收和荧光光谱可以计算出太阳能聚光板的内部量子效率(ηs,int，测定方法参见Nature Photonics,2018,12,105.)和外部量子效率(ηs,ext，测定方法参见Nature Photonics,2018,12,105.)。如图4所示，计算结果说明，该太阳能聚光板即使在较大尺寸(L＝100×100平方厘米)下，仍可保持极高的内部量子效率(ηs,int)>35％)；同时，其外部量子效率几乎不受器件尺寸的影响。该结果充分说明了CdTe-Pt(tpbp)体系可以有效地减小所制备聚光板的自吸收损失，从而实现较高的光学效率。
本发明太阳能聚光板主要由量子点作为光吸收材料，磷光有机分子作为光发射材料，聚合物作为光波导介质。利用量子点较大的消光系数高效吸光，并将能量转移到磷光有机分子，并通过其较大的光谱斯托克斯位移有效减小自吸收损失，最终通过聚合物光波导到侧面的太阳能电池实现光电转换。所述的磷光有机分子具有高效的磷光发射效率。作为优选方案，聚合物选用聚乙烯吡咯烷酮(PVP)，量子点选用碲化镉(CdTe)，可与磷光有机分子Pt-tetraphenyltetrabenzoporphyrin(Pt(tpbp))实现最优化的光谱匹配，最终获得高达9％的外部量子效率。
综上所述，我们发明的这种基于量子点-磷光有机分子杂化材料的高效太阳能聚光板，可以有效地减小荧光光子在波导过程中的自吸收损失，最终实现较高的光学效率。该发明对今后基于量子点的高性能太阳能聚光板研发具有极大的指导价值和意义。
Claims (3)
1.一种基于量子点-磷光有机分子杂化材料的太阳能聚光板，包括波导层，其特征在于：该太阳能聚光板波导层由量子点、磷光有机分子和聚合物混合而成，其中，量子点作为光吸收体，由尺寸为1-20纳米的半导体颗粒组成，于波导层中的摩尔比例控制在1-10%；磷光有机分子作为光发射体，具有高效的磷光发射效率，于波导层中的摩尔比例控制在3%-30%；聚合物为光波导介质，具有10000-1000000的分子量，于波导层中的摩尔比例控制在60-96%；所述的磷光有机分子为Platinum octaethylporphyrin (Pt(oep))、Pt-tetraphenyltetrabenzoporphyrin (Pt(tpbp))、Bis[2-(2-pyridinyl-N)phenyl-C](acetylacetonato)iridium(III) (Ir(ppy)2(acac))及它们衍生物中的一种或二种以上；所述的量子点组成为磷化铟、硒化铅、碲化铅中的一种或二种以上或下述三类物质中的一种或二种以上：
第一类：元素周期表中第二副族元素与第六主族元素组成的化合物中的一种或二种以上；所述第二副族元素为锌、镉或汞中的一种或二种以上，所述第六主族元素为硫、硒或碲中的一种或二种以上；
或第二类：三卤素钙钛矿量子点，具有ABX3结构，其中A=Cs，CH3NH3，或CH(NH2)2；B=Pb或Sn；X= Cl, Br或I中的一种或两种以上；
或第三类：铜和/或锰元素掺杂的上述第一类和/或第二类量子点，掺杂量在1-20%元素摩尔比。
2.根据权利要求1所述的太阳能聚光板，其特征在于：所述的聚合物为聚乙烯吡咯烷酮（PVP）、聚乙烯醇（PVA）或聚甲基丙烯酸甲酯（PMMA）中的一种或二种以上。
3.根据权利要求2所述的太阳能聚光板，其特征在于：所述的聚合物为聚乙烯吡咯烷酮（PVP）。
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