多酸基无机光敏剂在p-型染料敏化太阳能电池领域的应用

发布时间：2018-09-09 14:53

【摘要】：近年来,能源危机日益严峻,而染料敏化太阳能电池(DSSCs)作为目前众多的太阳能器件中最有前途的低成本、易组装和高效率的器件之一,引起了众多学者的关注。p-型染料敏化太阳能电池(p-DSSCs)是DSSCs的一个重要分支,是通过敏化光阴极将太阳能转化为电能。光敏剂是p-DSSCs的关键组分,目前光敏剂高昂的价格直接影响了p-DSSCs的实际应用,因此通过新型材料的设计开发替代其中的昂贵的金属和有机分子是p-DSSCs商业化的关键,所以开发低成本的p-型光敏剂也就势在必行。多金属氧酸盐是一种基于丰产元素Mo和W等元素通过常规法或者水热法等方法合成制备的绿色无毒的无机材料,部分多酸如过渡金属取代的多金属氧酸盐(TMSPs)具有优异的光电等性质:优异的热稳定性、良好的氧化还原稳定性、在紫外-可见区良好的光吸收性能、符合p-型光敏剂要求的HOMO和LUMO能级等。因此,TMSPs等可以作为p-型光敏剂开发低成本的p-DSSCs。本文中,我们对Keggin-型TMSPs、Dawson-型TMSPs以及有机羧酸基团修饰的Lindqvist-型多酸作为p-DSSCs的光敏剂进行了研究,做了如下的工作:1、三种 Keggin-型 TMSPs TBA8Na2[SiW9O37{Co(H2O)3}]· 11H20(SiW9CO3,(n-C4H9)4N+缩写为 TBA)、TBA4[(SiO4)W10MnⅢ2O36H6]·1.5CH3CN·2H2O(SiW_(10)Mn_2~Ⅲ)和TBA3.5H5.5[(SiO4)W10MnⅢ/Ⅳ2036]· 10H2O· 0.5CH3CN(SiW10MnⅢ/Ⅳ2)首次作为纯无机光敏剂被成功的引入到 p-DSSCs 中。SiW_9Co_3 敏化 p-DSSC 的 Voc=81mV,Jsc=1.60mA/cm2,FF=0.30,PCE=0.038%;SiW_(10)Mn_2~Ⅲ敏化p-DSSC 的 Voc=79mV,Joc=1.28mA/cm2,FF=0.29,PCE=0.029%;SiW10MnⅢ/Ⅳ2 敏化 p-DSSC 的 Voc=93mV,Jsc=0.88mA/cm2,FF=0.34,PCE=0.027%。三者的效率都超过了 C343 0.017%的效率。这是低成本的多酸作为纯无机光敏剂首次应用在p-DSSCs中,为p-DSSCs领域光敏剂特别是无机光敏剂的设计开发开辟了新的路径。此外,它们也扩大了多酸的应用范围。2、两种Dawson-型TMSPs光敏剂P_2W_(17)Co和P_2W_(17)Mn首次被成功的引入到p-DSSCs中。我们测试和计算了他们的热稳定性、UV-Vis吸收光谱以及二者的LUMO和HOMO 能级等性质。P_2W_(17)Co 敏化的 p-DSSC 的 Voc=101mV,Jsc=1.285mA/cm2,FF=0.313,PCE=0.0406%;P_2W_(17)Mn 敏化的 p-DSSC 的 Voc=84mV,Joc=1.268mA/cm2,FF=0.296,PCE=0.0315%;P_2W_(17)Co/P_2W_(17)Mn共敏化的 p-DSSC 的 Voc=102mV,Jsc=1.49 mA/cm2,FF=0.305,PCE=0.0464%。这是过渡金属取代的Dawson-型多酸作为光敏剂和共敏剂首次应用在构筑低成本的p-DSSCs中,也为Dawson-型过渡金属取代的多金属氧酸盐材料在能源领域找出了一个新的很有潜力的方向。3、一种Lindqvist-型多酸TBA2[Mo_6O_(19)]和一种有机羧酸基团修饰的Lindqvist-型多酸TBA2[MO6O18-(N-C6H4-3-COOH)]首次被作为p-DSSCs的光敏剂进行了研究。测试表明多酸光敏剂 TBA2[MO6O18-(N-C6H4-3-COOH)]敏化 p-DSSCs的Voc=101mV,Joc=0.648 mA/cm2,FF=0.305,PCE=0.0200%;多酸光敏剂 TBA2[MO6O19]敏化 p-DSSCs 的 Voc=76 mV,Jsc=0.266 mA/cm2,FF=0.241,PCE=0.00486%。其中,与 TBA2[MO6019]敏化 p-DSSCs相比,多酸光敏剂 TBA2[MO6018-(N-C6H4-3-COOH)]敏化 p-DSSCs 的PCE提高了 311.5%,Voc提高了 32.9%,,Jsc提高了 143.9%,FF提高了 26.6%。这表明羧基的存在很有可能促进了多酸光敏剂和NiO之间空穴的注入,修饰后的多酸光捕获能力的增强也有利地促进了电池效率的提高。
[Abstract]:In recent years, the energy crisis has become increasingly serious. As one of the most promising low-cost, easy-to-assemble and high-efficiency solar devices, dye-sensitized solar cells (DSSCs) have attracted the attention of many scholars. p-type dye-sensitized solar cells (p-DSSCs) are an important branch of DSSCs and are sensitized by photocathodes. Photosensitizers are the key components of p-DSSCs. The high price of photosensitizers directly affects the practical application of p-DSSCs. Therefore, it is the key to commercialize p-DSSCs to develop low-cost p-type photosensitizers through the design and development of new materials to replace the expensive metals and organic molecules. Polyoxometalates are green and nontoxic inorganic materials synthesized by conventional or hydrothermal methods based on High-yield elements Mo and W. Some polyoxometalates, such as transition metal substituted polyoxometalates (TMSPs), have excellent photoelectric properties, such as excellent thermal stability, good redox stability, and in purple. In this paper, we studied Keggin-type, Dawson-type and organic carboxylic acid modified Linqvist-type polyacids as photosensitizers for p-DSSCs. The following work has been done: 1. Three Keggin-type TMSPs TBA8Na2 [SiW9O37{Co(H2O))3}].11H20 (SiW9CO3, (n-C4H9)4N+ abbreviation for TBA), TBA4 [(SiO4) W10MnIII 2O36H6]..1.5CH3CN 2H2O (SiW_ (10) Mn_2~III) and TBA3.5H 5 [(SiO4) W110MnIII/IVIVH 3 3 MnIII]. H 2O2036]. 10 H 2O3 H 2O 3 [(SiO4) MnIII / IVH 4 H 4 H 4 H 9) 4N + abbrebrebreviation for TBA), TBA4 [(SiW 4 (SiO 4(IV2) Successfully introduced as a pure inorganic photosensitizer for the first time In p-DSSC, Voc = 81 mV, Jsc = 1.60mA/cm2, FF = 0.30, FF = 0.30, PCE = 0.038%; Voc = 79 mV, Joc = 1.28 mA/cm2, FF = 0.29, PCE = 0.029%; Voc = 93mV, Joc = 1.28 mA/cmA/c2, FF = 0.29, PCE = 0.029%;SiW10MnIII/IV2, Voc = 93 mV, 93 mV = 93mV, 93 mA/c = 93 mA/c = 93 mV, Joc = 1.28mA/c = 0.28mA/c2, FF = 0.28mA/cmA/c2, FF = 0.2, FF = 0.34, PCE = 0.027%. The efficiency of all three is higher than that of C343 0.017%. This is low. Cost-effective polyoxometalates were first used as pure inorganic photosensitizers in p-DSSCs, opening up a new path for the design and development of photosensitizers in p-DSSCs, especially inorganic photosensitizers. In addition, they also extended the application range of polyoxometalates. 2. Two Dawson-type TMSPs photosensitizers, P_2W_ (17) Co and P_2W_ (17) Mn, were successfully introduced into p-DSSCs for the first time. The thermal stability, UV-Vis absorption spectra and the properties of both LUMOand HOMOenergy levels were measured and calculated.Voc = 101mV, Jsc = 1.285mA/cm2, FF = 0.313, PCE = 0.0406%;Voc = 84mV, Joc = 1.268mA/cm2, FF = 0.296, PCE = 0.0315%;Voc = 84 mV, Joc = 1.268mA/cm2, FF = 0.296, PCE = 0.0315%; (P u uu (17) Mnsensitized P (17) Co sensitized P (17) sensitized P (17) Co sensitized P (17) (17) Co-sensitized p-D with Mn Voc = 102 mV, Jsc = 1.49 mA / cm2, FF = 0.305, PCE = 0.0464%. This is the first time that transition metal-substituted Dawson-type polyoxometalates have been used as photosensitizers and co-sensitizers in the construction of low-cost p-DSSCs. It also finds a new and promising direction in the energy field for Dawson-type transition metal-substituted polyoxometalates. Dqvist-type polyacid TBA2 [Mo_6O_ (19)] and an organic carboxylic acid group modified indqvist-type polyacid TBA2 [MO6O18 - (N-C6H4-3-COOH)] were first used as a photosensitizer for p-DSSCs. Tests showed that the polyacid photosensitizer TBA2 [MO6O18 - [MO6O18 - (N-C 6H4-3-COOH)] sensitized p-DSSCVoc = 101mV, Joc = 0.648, Joc = 0.648 / cm2, FFA / cm2, FFA / cm2, FFA / cm2, FFA / cm2, FFA = 0.305, FF PCE = 0.0200.020, 0%; polyacid photosensitivity Compared with TBA2 [MO6019] sensitized p-DSSCs, the PCE of polyacid photosensitizer TBA2 [MO6018- (N-C6H4-3-COOH)] sensitized p-DSSCs was 311.5%, 32.9%, 32.9%, 32.9%, 32.9%, 32.9%, 32.9%, JFF143.3.3%, 143.3.9%, 26.9%, 26.6% and 26.6% higher than that of TBA2 [MO6019]sensitized p-DSSC.In the meantime, it is necessary to study the relationship between the two. It may promote the injection of holes between poly-acid photosensitizer and NiO, and the enhancement of the light capture ability of the modified poly-acid photosensitizer can also improve the efficiency of the battery.
【学位授予单位】：东北师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TM914.4

【相似文献】