CN101928469A - 有机染料及使用此有机染料的染料敏化太阳能电池 - Google Patents
有机染料及使用此有机染料的染料敏化太阳能电池 Download PDFInfo
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Abstract
本发明公开了一种有机染料及使用此有机染料的染料敏化太阳能电池。所述用于染料敏化太阳能电池的有机染料具有通式(1):,其中Ar1为经取代或未取代的亚芳基,Ar2、Ar3各为经取代或未取代的芳基,Sp1为单键或使Ar1与呋喃基共轭的间隔基,Sp2为单键或使呋喃基与Ac共轭的间隔基,Ac是电子受体基,且Y是固定基。其中,当Ar2或Ar3为经取代的芳基时,其上的取代基是选自由碳数1~5的烷基与碳数1~5的烷氧基所组成的组。本发明所提出的含呋喃片段的DSSC用有机染料可具有十分接近现有的钌基染料的效能,但因不须使用钌这种贵重金属,故其成本远低于后者。
Description
技术领域
本发明是有关于一种太阳能电池材料,且特别是有关于一种用于染料敏化太阳能电池(Dye-Sensitized Solar Cell,DSSC)的有机染料,以及使用此有机染料的DSSC。
背景技术
为应对能源供应与化石燃料消耗所致的环境问题,全球都在研发干净、可再生的能源。在多种化石燃料的替代方案中,太阳能明显是较佳的,只要有效率达10%的太阳能转换系统覆盖全球陆地的0.16%,即足以提供全世界消耗的化石燃料能量的两倍。虽然硅或其他半导体基的太阳能电池(光伏打电池)已主导太阳能电池市场数十年,但自从等人获得技术上突破(例如O’Regan,B.;M.Nature 1991,353,737)以来,染料敏化太阳能电池(DSSC)也已受到相当注意,其中钌基DSSC转换效率约可达11%。无金属DSSC的发展虽晚于钌基DSSC,但亦已受到颇多注目,其效率约可达9%。
历来已有多种无金属染料用于制作DSSC。发明人之前曾报导过由作为电子供体的芳胺基、作为电子受体的2-氰基丙烯酸基、含噻吩片段的共轭桥接基所构成的无金属染料(K.R.Justin Thomas,J.T.Lin,Y.-C.Hsu and K.-C.Ho,Chem.Commun.2005,4098)。与类苯(benzenoid)片段相比之下,噻吩片段可提供更有效的共轭,并降低电荷转移跃迁的能量,因其共振能量较小(29kcal·mol-1,苯为36kcal·mol-1)。
由此可见,如使染料分子的桥接基具有共振能量更小(26kcal·mol-1)的呋喃片段,其效果十分令人期待。
发明内容
本发明提供一种用于染料敏化太阳能电池的有机染料,其桥接基具有呋喃片段。
本发明还提供一种染料敏化太阳能电池,其是使用本发明的有机染料制作而得。
本发明的用于DSSC的有机染料由通式(1)所表示:
其中Ar1为经取代或未取代的亚芳基(arylene),Ar2、Ar3各为经取代或未取代的芳基(aryl),Sp1为单键或使Ar1与呋喃基共轭的间隔基,Sp2为单键或使呋喃基与Ac共轭的间隔基,Ac是一电子受体基,且Y是一固定基,其中,当Ar2或Ar3为经取代的芳基时,其上取代基是选自由碳数1~5的烷基与碳数1~5的烷氧基所组成的组。
在一实施例中,上述Ar1为经取代或未取代的1,4-苯基、2,7-芴基(2,7-fluorene)或2,7-咔唑基(2,7-carbazole)。经取代的1,4-苯基、2,7-芴基或2,7-咔唑基上的取代基可选自由碳数1~5的烷基与碳数1~5的烷氧基所组成的组。其中,1,4-苯基的2-位置与5-位置中可有至少其一被烷基或烷氧基取代,2,7-芴基的9-位置可以被至少一个烷基取代,例如是被两个乙基取代。
在一实施例中,上述Ar2及Ar3各自独立为经取代或未取代的苯基、2-芴基(2-fluorenyl)、1-萘基(1-naphthyl)、9-蒽基(9-anthracenyl)、1-芘基(1-pyrenyl)或2-咔唑基(2-carbazolyl)。Ar2及Ar3可同时为苯基或2-芴基。
在一实施例中,上述间隔基Sp1、Sp2各自为伸乙烯基(vinylene)、氰基伸乙烯基(cyanovinylene)或2,5-噻吩基(2,5-thiophene group)。
在一实施例中,上述电子受体基Ac为2-氰基乙烯基。
在一实施例中,上述固定基Y包括一羧酸基。
在一实施例中,上述电子受体基Ac与固定基Y的组合包括2-氰基丙烯酸基。
在一些实施例中,上述用于染料敏化太阳能电池的有机染料分别具有下式(2)、(3)、(4)、(5)所示的分子结构,其中Ar2与Ar3各自的4-位置可被碳数1~5的烷基与碳数1~5的烷氧基取代。
本发明的染料敏化太阳能电池包括上述本发明的有机染料、电解质,以及光电极。
本发明提出的含呋喃片段的DSSC用有机染料可具有十分接近现有的钌基染料的效能,但因无须使用钌这种贵重金属,故其成本远低于后者。
下面通过附图和实施例,对本发明的技术方案做进一步的详细描述。
附图说明
图1显示分别使用染料化合物1~4的DSSC的光电流-电压(J-V)曲线。
图2显示分别使用染料化合物1~4的DSSC在不同波长下的光电流转换效率。
具体实施方式
本发明的用于DSSC的有机染料由通式(1)所表示:
其中Ar1为经取代或未取代的亚芳基(arylene),Ar2、Ar3各为经取代或未取代的芳基,Sp1为单键或使Ar1与呋喃基共轭的间隔基,Sp2为单键或使呋喃基与Ac共轭的间隔基,Ac是一电子受体基,且Y是一固定基,其中,当Ar2或Ar3为经取代的芳基时,其上的取代基是选自由碳数1~5的烷基与碳数1~5的烷氧基所组成的组。
上述Ar1可为经取代或未取代的1,4-苯基、2,7-芴基或2,7-咔唑基。经取代的1,4-苯基、2,7-芴基或2,7-咔唑基上的取代基可选自由碳数1~5的烷基与碳数1~5的烷氧基所组成的组。其中,1,4-苯基的2-位置与5-位置中可有至少其一被烷基或烷氧基取代,2,7-芴基的9-位置可被至少一个烷基取代,例如是被两个乙基取代。上述Ar2及Ar3可各自独立为经取代或未取代的苯基、2-芴基、1-萘基、9-蒽基、1-芘基或2-咔唑基。Ar2及Ar3可同时为苯基或2-芴基。当Ar2及Ar3同为苯基时,Ar2与Ar3各自的4-位置可被碳数1~5的烷基与碳数1~5的烷氧基取代。上述间隔基Sp1、Sp2各自可为伸乙烯基(vinylene)、氰基伸乙烯基(cyanovinylene)或2,5-噻吩基(2,5-thiophene group)。另外,上述电子受体基Ac与固定基Y的组合可为2-氰基丙烯酸基。
<实例>
本发明的有机染料的4个实例为以下化合物1~4。
化合物1~4可以下示合成架构1来合成。
合成架构1:
化合物1、3的合成皆以具有三苯胺片段或二苯胺基-2-芴片段的Wittig试剂开始。Wittig试剂与2-呋喃醛反应形成中间体1b与3b,其再进行甲酰化而形成1c与3c,接着令1c(3c)与氰基乙酸进行Knoevenagel缩合反应,即得所需化合物1(3)。至于化合物2/4的合成,则是以5-溴-2-呋喃醛与适当的苯硼酸/锡烷化合物进行Suzuki耦合/Stille耦合反应,而形成中间体2b/4b,再令中间体2b/4b与氰基乙酸反应而形成所需化合物2/4。
化合物1~4溶于四氢呋喃(THF)时的吸收与发射特性的资料请见表1。
表1:染料的光学参数、氧化还原电位与DSSC效能参数a,b
a光吸收与电化学资料在THF溶液中收集;扫描速率100mV·s-1;电解质为(n-C4H9)4NPF6;ΔEp为阳极峰与阴极峰的间距;电位是以二茂铁内标物(E1/2=+265mV对Ag/AgNO3)为参考而得的。
b使用在FTO(7Ω/sq)基板上厚度约15μm、工作面积0.25cm2的TiO2光电极进行实验。
cN719为现有技术中由以下化合物(即N3染料)的2价阴离子与2当量的四正丁基铵离子所形成的染料:
dVOC:开路电压,为太阳能电池所能提供的最大电动势。
eJSC:闭路电流,为太阳能电池在线路接通时所能提供的最大电流。
fff:填充因子(fill factor),为电池实际使用时的最大功率与理论最大功率的比值。
gη:光电转换效率(energy conversion efficiency)。
约在400~600nm的主吸收带可归因于π-π*轨域与电荷转移跃迁的重叠。这些化合物的电荷转移特征亦可由其吸收带与发射带(3225~4895cm-1)之间的Stokes位移得证。负的溶剂化显色(solvatochromism)效应,即电荷转移带于极性较高溶剂中的蓝位移,亦可见于这些化合物。例如,化合物1在甲苯及乙腈中的最大吸收波长分别为485nm及439nm。此现象可归因于羧酸的去质子化,其降低了电子受体的强度。
对各化合物而言,在其循环伏安测量时所见的半可逆波形(表1中的E氧化)可归因于芳胺片段的氧化。因为化合物1、2的分子长度较短,故拉电子的电子受体对芳胺片段的影响较大,而提高了芳胺片段的氧化电位。这些化合物的激发态电位(E0-0 *)为-0.74~-0.80V(相对于标准氢电极),是由E氧化及从吸收带边缘的0-0能阶激发能量(zero-zero excitation energy,E0-0)得知,其负值比TiO2电极的导带边缘能量位准(对标准氢电极为-0.5V)更大,而得以确保电子注入过程从能量观点来看上是容易发生的。
接着,使用作为集光敏化剂的上述染料、锐钛矿TiO2纳米晶体颗粒及作为电解质的0.05M I2/0.5M LiI/0.5M三级丁基吡啶的乙腈溶液,制作有效面积0.25cm2的DSSC。所得的DSSC在AM 1.5照明下的装置性能统计资料列于表1,光电流-电压(J-V)曲线显示于图1,在不同波长下的光电流转换效率(IPCE)则显示于图2。这些DSSC具有很高的转换效率(6.12~7.36%),其最佳的甚至可达到在类似条件下以N719制作的DSSC的转换效率(7.69%)的96%。
DSSC转换效率的高低顺序为染料化合物1>2>3>4,是受到几项因素影响:(a).较低的最高填充分子轨域(HOMO,由循环伏安法[CV]估算而得)有利于被氧化染料的还原,并抑制从TiO2至染料的反向电子转移,进而导致较大的VOC与JSC(化合物1、2);(b).在较长波长区域有较大吸收的化合物可具有较佳的光能收获(化合物1>2);(c).较高的TiO2上染料吸附密度(化合物1/2/3/4为4.5/4.1/3.8/4.6×10-7mol·cm-2)较有利于光能收获,故化合物1>2>3。另外,光注入电子与被氧化染料的再结合生命期(τR)也有以开路下的瞬间光电压来测量,结果化合物1、2、3、4及N719的τR分为4.9ms、5.8ms、4.3ms、3.1ms、10.4ms。此现象与上述电池效率的变化趋势相符。
以下为上述化合物1与先前提出的噻吩同类物3-(5-(4-(二苯胺基)苯乙烯基)噻吩-2-基)-2-氰基丙烯酸(D5)的比较。与乙腈中的化合物1相较(λ吸收=439nm(33000M-1cm-1),TiO2吸附密度=4.5×10-7mol·cm-2),D5于乙腈中虽有稍佳的光能收获(λ吸收=476nm(37600M-1·cm-1))及TiO2吸附密度(4.8×10-7mol·cm-2),但以化合物1制作的DSSC的效能优于在类似条件下以D5制作的(VOC=0.64V,JSC=14.61mA·cm-2,ff=0.65,η=6.09%)。此现象的原因可能是:D5的τR(4.3ms)较短、非键结分子间硫-硫交互作用有害于被激发染料对TiO2的电子注入、噻吩片段稍较容易捕陷电子等。
综上所述,本发明所提出的含呋喃片段的DSSC用有机染料可具有十分接近现有的钌基染料的效能,但因不须使用钌这种贵重金属,故其成本远低于后者。
最后应说明的是:以上实施例仅用以说明本发明的技术方案而非对其进行限制,尽管参照较佳实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对本发明的技术方案进行修改或者等同替换,而这些修改或者等同替换亦不能使修改后的技术方案脱离本发明技术方案的精神和范围。
Claims (17)
2.根据权利要求1所述的用于染料敏化太阳能电池的有机染料,其中Ar1为经取代或未取代的1,4-苯基、2,7-芴基或2,7-咔唑基。
3.根据权利要求2所述的用于染料敏化太阳能电池的有机染料,其中经取代的1,4-苯基、2,7-芴基或2,7-咔唑基上的取代基是选自由碳数1~5的烷基与碳数1~5的烷氧基所组成的组。
4.根据权利要求3所述的用于染料敏化太阳能电池的有机染料,其中所述1,4-苯基的2-位置与5-位置中至少其一被烷基或烷氧基取代。
5.根据权利要求3所述的用于染料敏化太阳能电池的有机染料,其中所述2,7-芴基的9-位置被至少一个烷基取代。
6.根据权利要求5所述的用于染料敏化太阳能电池的有机染料,其中所述2,7-芴基的9-位置被两个乙基取代。
7.根据权利要求1所述的用于染料敏化太阳能电池的有机染料,其中Ar2及Ar3各自独立为经取代或未取代的苯基、2-芴基、1-萘基、9-蒽基、1-芘基或2-咔唑基。
8.根据权利要求7所述的用于染料敏化太阳能电池的有机染料,其中Ar2及Ar3同时为苯基或2-芴基。
9.根据权利要求1所述的用于染料敏化太阳能电池的有机染料,其中所述间隔基Sp1、Sp2各自为伸乙烯基、氰基伸乙烯基或2,5-噻吩基。
10.根据权利要求1所述的用于染料敏化太阳能电池的有机染料,其中所述电子受体基Ac为2-氰基乙烯基。
11.根据权利要求1所述的用于染料敏化太阳能电池的有机染料,其中所述固定基Y包括一羧酸基。
12.根据权利要求1所述的用于染料敏化太阳能电池的有机染料,其中所述电子受体基Ac与所述固定基Y的组合包括2-氰基丙烯酸基。
17.一种染料敏化太阳能电池,包括根据权利要求1~16中任一权利要求所述的用于染料敏化太阳能电池的有机染料、电解质、以及光电极。
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