CN108074749A - 虾青素用作共敏剂在染料敏化太阳能电池中的应用 - Google Patents
虾青素用作共敏剂在染料敏化太阳能电池中的应用 Download PDFInfo
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Abstract
本发明针对卟啉类染料敏化太阳能电池中卟啉染料捕光效率低和自身聚集、暗电流严重，从而影响光电转化效率的问题，将虾青素首次引入作为共敏剂，填补了卟啉的光学窗口，使得卟啉类染料敏化太阳能电池的光捕获效率提高、暗电流降低，从而提高了电池的光电转化效率。和已用于卟啉类染料敏化太阳能电池的各种共敏化剂相比，本发明所用虾青素不仅有效的提高了电池的光电转化效率，而且不需要任何繁琐的合成步骤，生产过程绿色清洁，天然价廉，丰富易得，自身清洁绿色，对生物和环境无害，具有广阔的应用前景。
Description
技术领域
本发明涉及虾青素作为共敏剂在染料敏化太阳能电池中的应用。
背景技术
人类能源需求不断提高，成本低廉、环境友好的高效能源转化和利用方式亟待开发。染料敏化太阳能电池1991年以来发展迅速，其中光敏染料是核心[参见：(a)O′Regan，B.；Gratzel，M.Nature.1991，353，737；(b)Hardin，B.E.；Snaith，H.J.；McGehee，M.D.Nat.Photonics.2012，6，162]。第一代钌吡啶类光敏染料敏化的太阳能电池在标准条件(100mW cm-2功率和AM1.5辐照的太阳光模拟器照射)下，光电转化效率达到11.4％[参见：(a)Gao，F.；Wang，Y.；Shi，D.；Zhang，J.；Wang，M.；Jing，X.；Humphry-Baker，R.；Wang，P.；Zakeeruddin，S.M.；Gratzel，M.J.Am.Chem.Soc.2008，130，10720；(b)Chen，C.；Wang，M.；Li，J.；Pootrakulchote，N.；Alibabaei，L.；Ngoc-le，C.；Decoppet，J.；Tsai，J.；Gratzel，C.；Wu，C.；Zakeeruddin，S.M.；Gratzel，M.ACS Nano.2009，3，3103；(c)Yu，Q.；Wang，Y.；Yi，Z.；Zu，N.；Zhang，J.；Zhang，M.；Wang，P.ACS Nano.2010，4，6032；(d)Chiba，Y.；Islam，A.；Watanabe，Y.；Komiya，R.；Koide，N.；Han，L.Y.Jpn.J.Appl.Phys.Part 22006，45，L638.]。鉴于钌吡啶类光敏染料所需金属钌价格昂贵、资源有限，非贵金属和纯有机染料敏化太阳能电池被普遍认为更有发展前途。卟啉是叶绿素的关键结构，卟啉类光敏染料无贵金属，来源丰富、成本低廉、环境友好、光、热、化学稳定性和生物相容性好，已成为染料敏化太阳能电池领域的主流光敏染料，现报道的光电转化效率最高值已达13％[参见：(a)Yella，A.；Lee，H.-W.；Tsao，H.N.；Yi，C.；Chandiran，A.K.；Nazeeruddin，M.K.；Diau，E.W.-G.；Yeh，C.-Y.；Zakeeruddin，S.M.；M.Science.2011，334，629；(b)Li，L.-L.；Diau，E.W.-G.Chem.Soc.Rev.2013，42，291；(c)Mathew，S.；Yella，A.；Gao，P.；Humphry-Baker，R.；Curchod，B.F.E.；Ashari-Astani，N.；Tavernelli，I.；Rothlisberger，U.；Nazeeruddin，M.K.；M.Nat.Chem.2014，6，242；(d)Urbani，M.；Gratzel，M.；Nazeeruddin，M.K.；Torres，T.Chem.Rev.2014，114，12330.]。
但卟啉自身具有两大缺陷，一是在550nm附近有光学窗口，限制了太阳光的充分捕捉；二是分子易聚集，增加了暗电流，降低了电池效率。共敏剂常被用于填补卟啉的光学窗口，增加吸光效率，并阻止分子聚集，提高电池效率。以卟啉类光敏染料YD2-o-C8敏化的太阳能电池，加入共敏剂Y123，效率从8％左右提高到9.4％；以卟啉类光敏染料XW4敏化的染料敏化太阳能电池，加入共敏剂C1，效率从7.9％提高到10.45％；以纯有机分子ADEKA-1为光敏染料的染料敏化太阳能电池，加入共敏化剂LEG4，效率从12％提高到14.3％[参见：(a)Yella，A.；Lee，H.-W.；Tsao，H.N.；Yi，C.；Chandiran，A.K.；Nazeeruddin，M.K.；Diau，E.W.-G.；Yeh，C.-Y.；Zakeeruddin，S.M.；M.Science.2011，334，629；(b)Wang，Y.；Chen，B.；Wu，W.；Li，X.；Zhu，W.；Tian，H.；Xie，Y.Angew.Chem.Int.Ed.2014，53，10779；(c)Kakiage K.；Aoyama，Y.；Yano T.；Oya K.；Fujisawa J.；Hanaya M..Chem.Commun.，2015，51，15894.]
虾青素(英语：Astaxanthin)，化学名称是3，3′-二羟基-4，4′-二酮基-β，β′-胡萝卜素，是类胡萝卜素的一种，化学结构通式为：
在每个双键位置均有顺反异构，因此具有多个异构体。其中一些异构体是天然产物，光学纯品可通过，但不仅限于，人工繁殖雨生红球藻(pluvailis)大量方便的提取，来源丰富、制备廉价、环境和生物友好。在二甲基亚砜溶液中的紫外-可见光谱吸收峰处于550nm，正好位于卟啉类光敏染料的光学窗口。[参见：(a)Olsina J.；Durchan M.；MinofarB.；Polivka T.；Manal T.arXiv：1208.4958[physics.chem-ph]]。
类胡萝卜素在绿叶的光合作用中起到重要作用，受此启发，被用在卟啉类染料敏化太阳能电池中充当共敏剂，在同样的组装和测试条件下，可将电池效率从3.1％提高到4.0％，提高了29％，是一种有效的共敏化剂；类胡萝卜素共轭双键长度对电池效率的影响也被研究，在双键个数为9-13的范围内，共轭链越长，电池效率越高[参见：Xiao-Feng WangX-F.；Xiang J.；Wang P.；Koyama Y.；Yanagida S.；Wada Y.；Hamada K.；Sasaki S.；Tamiaki H.Chem.Phys.Lett.2005，408，409.]但具有13个双键的天然产物虾青素尚未被用于制备染料敏化太阳能电池。
发明内容
本发明的目的在于使用天然、绿色、价廉、易得的虾青素作为一种新型的共敏剂，解决敏化太阳能电池中染料捕光效率低和自聚集，从而影响光电转化效率的问题。
本发明解决该问题的技术方案：将虾青素作为共敏化剂，与卟啉类染料共同吸附到纳米二氧化钛上作为光敏层，填补卟啉的光学窗口，提高可见光捕获效率，降低卟啉染料自身的分子聚集，从而提高染料敏化太阳能电池的光电转化效率。
本发明的实施效果
共敏剂虾青素在卟啉光学窗口吸收光线，使得同样组装和测试条件下的卟啉类DSSC的光捕获效率提高、暗电流降低，从而表现为使电池的光电转化效率提高约32％，最高效率达到14.1％
与已用于染料敏化太阳能电池的各种共敏化剂相比，本发明所用虾青素天然价廉，丰富易得，而且有效的提高染料敏化太阳能电池的光电转化效率。具体体现为：
1.不需要任何繁琐的有机合成步骤，生产过程绿色清洁，天然价廉，丰富易得；
2.自身清洁绿色，对生物和环境无害；
3.更加有效的提高了染料敏化太阳能电池的光电转化效率。
具体实施方式
下面结合具体实施案例对本发明作进一步描述，将有助于对本发明的理解。但并不能以此来限制本发明的权利范围，而本发明的权利范围应以权利要求书阐述的为准。
本发明实施例中，虾青素(左旋，纯度＞97％)、二氧化钛光阳极、铂电极和30μm厚度的聚酰亚胺胶带均为市售。标志性的高效卟啉类光敏染料CM-b和YD2-o-C8的结构和合成方法参考文献[参见Li C.；Luo L.；Wu D.；Jiang R.；Lan J.；Wang R.；Huang L.；Yang S.；You J.；.J.Mater.Chem.A，2016，2016，4，11829]自制。
光谱表征所用仪器为：HITACHI U-2910型紫外-可见分光光度计(扫描范围250～1100nm)。光电化学特性表征所用仪器为：光电转化效率用Oriel 94023A，Newport Corp.太阳光模拟器提供功率为100mW cm-2的条件下，用Keithley Series 2000型点位表测得光电流密度-电压曲线。单色光电转化效率在QTest Station 1000AD(Crowntech，Inc.)上测试。
实施例1：虾青素/CM-b共敏化电池的制备。用氯仿/无水乙醇(4/6，v/v)为溶剂，配制浓度为0.1mM的虾青素和0.1mM的CM-b混合溶液，为着色染料溶液。将二氧化钛光阳极浸入着色染料溶液中，在35℃下避光静置24小时。随后取出泡好的二氧化钛光阳极并用二氯甲烷/无水乙醇(1/1，v/v)混合溶液冲洗，空气下自然晾干，得到染料敏化的二氧化钛光阳极。再用聚酰亚胺胶带将染料敏化的二氧化钛光阳极和铂电极粘合，注入电解质溶液，制备出染料敏化太阳能电池。
实施例2：用于对照的CM-b电池的制备。用氯仿/无水乙醇(4/6，v/v)为溶剂，配制浓度为0.1mM的CM-b溶液，为着色染料溶液。将二氧化钛光阳极浸入着色染料溶液中，在35℃下避光静置24小时。随后取出泡好的二氧化钛光阳极并用二氯甲烷/无水乙醇(1/1，v/v)混合溶液冲洗，空气下自然晾干，得到染料敏化的二氧化钛光阳极。再用聚酰亚胺胶带将染料敏化的二氧化钛光阳极和铂电极粘合，注入电解质溶液，制备出染料敏化太阳能电池。
实施例3：染料敏化太阳能电池的光电转化效率测试。室温条件，在可见光波长范围的单色光照射下，测试实施例1和2所得的染料敏化太阳能电池单色光电转化效率。测得虾青素/CM-b共敏化电池比用于对照的CM-b电池，在413-670nm波长范围内，峰值同为93％，谷值从74％提高到了85％，很好的填补了卟啉染料CM-b的光学窗口，从而具有更好光捕获能力。
室温条件，在100mW cm-2功率的AM1.5的太阳光模拟器照射下，测试实施例1和2所得的染料敏化太阳能电池参数。测得虾青素/CM-b共敏化电池比用于对照的CM-b电池的光电流密度从22.58mA cm-2提高到25.3mA cm-2，开路电压从0.734V提高到0.772V，填充因子分别为64.6％和72.1％，光电转换效率从10.7％提高到14.1％，提高了32％。
实施例4：虾青素/YD2-o-C8共敏化电池和用于对照的YD2-o-C8电池的制备及光电性能测试。与实施例1和2的制备方法同样，只是将着色染料溶液中的CM-b换成YD2-o-C8。
和实施例3的测试方法一样，单色光电转化效率测试结果表明虾青素/YD2-o-C8共敏化电池比用于对照的YD2-o-C8电池，在400-700nm波长范围内，峰值同为76％，谷值从58％提高到了72％，很好的填补了卟啉染料YD2-o-C8的光学窗口，从而具有更好光捕获能力。
电池参数测试表明，虾青素/YD2-o-C8共敏化电池比用于对照的YD2-o-C8电池的光电流密度从18.65mA cm-2提高到21.3mA cm-2，开路电压从0.705V提高到0.726V，填充因子分别为63.8％和74.2％，光电转换效率从8.5％提高到11.5％，提高了35％。
Claims (2)
1.虾青素作为共敏剂，用于染料敏化太阳能电池，提高光电转化效率。
2.如权利要求1所述虾青素的化学名称是3，3′-二羟基-4，4′-二酮基-β，β′-胡萝卜素，包括所有双键位置的顺反异构体，化学结构式如说明书背景技术部分所述。
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