CN109216033B - 一种量子点敏化太阳能电池用对电极材料的制备方法 - Google Patents
一种量子点敏化太阳能电池用对电极材料的制备方法 Download PDFInfo
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Abstract
一种量子点敏化太阳能电池用对电极材料的制备方法,将甲基橙和FeCl3·6H2O溶于去离子水中,然后加入吡咯单体,室温下搅拌,得到掺杂甲基橙的聚吡咯纳米管;将掺杂甲基橙的聚吡咯纳米管用去离子水和乙醇清洗后,在60℃真空烘箱中干燥,干燥后的掺杂甲基橙的聚吡咯纳米管与KOH混合均匀,然后在N2保护下热处理,冷却到室温后,清洗杂质;然后在80℃真空烘箱中烘干,得到相互连结氮/硫共掺杂多孔碳纳米片。优点是:该电极材料为相互连结的氮/硫共掺杂多孔碳纳米片结构,具有较高的比表面积和孔体积,以及包含微孔、介孔、大孔的多级孔结构,使其具有优异的电化学性能。
Description
技术领域
本发明涉及一种量子点敏化太阳能电池用对电极材料的制备方法。
背景技术
多孔碳材料具有比表面积大、孔结构可调、价格便宜、导电性高、稳定性好等特点,因此可作为量子点敏化太阳能电池对电极材料。但是,颗粒状多孔碳材料内容易形成较长的电解质扩散通道,这将限制电解质的传输速率,从而影响多孔碳材料的电化学性能。低维多孔碳材料,特别是二维(2D)多孔碳材料能够提供较短的电解质扩散通道和较快的电子传输过程。因此,作为量子点敏化太阳能电池对电极,石墨烯基纳米结构碳材料和多孔碳纳米片材料都表现出比颗粒状多孔碳材料优异的电化学性能。
另一方面,研究发现,氮、硫、磷、硼等元素掺杂,可以明显改善碳材料的表面浸润性,提高其电导性能和表面电催化性能。因此,掺杂碳材料使其具有优异的电化学性能成为目前电化学领域的主要研究方向。
发明内容
本发明要解决的技术问题是提供一种量子点敏化太阳能电池用对电极材料的制备方法,该电极材料为相互连结的氮/硫共掺杂多孔碳纳米片结构,具有较高的比表面积和孔体积,以及包含微孔、介孔、大孔的多级孔结构,使其具有优异的电化学性能。
本发明的技术解决方案是:
一种量子点敏化太阳能电池用对电极材料的制备方法,其具体步骤是:
(1)制备掺杂甲基橙的聚吡咯纳米管
按照重量分数计,将0.35份-0.65份的甲基橙(MO)和3份-6份的FeCl3·6H2O溶于去离子水中,得到甲基橙-氯化铁混合水溶液;然后将0.7份-1.4份吡咯单体加入甲基橙-氯化铁混合水溶液中,室温下搅拌18h-24h,得到掺杂甲基橙的聚吡咯(PPy)纳米管;
(2)将掺杂甲基橙的聚吡咯纳米管用去离子水和乙醇清洗后,在60℃真空烘箱中干燥,干燥后的掺杂甲基橙的聚吡咯纳米管与KOH按照重量比1:1-1:3混合均匀,得到纳米管/KOH混合物;然后将纳米管/KOH混合物在N2保护下升温到600℃-800℃,热处理1h-3h,冷却到室温后,用1mol/L HCl和去离子水清洗杂质;然后在80℃真空烘箱中烘干,得到相互连结氮/硫共掺杂多孔碳纳米片。
进一步的,步骤(1)中所述FeCl3·6H2O与去离子水的质量体积比为0.01g/mL-0.02g/mL。
进一步的,热处理时,升温速率为3℃/min-10℃/min。
进一步的,所述相互连结氮/硫共掺杂多孔碳纳米片具有多级孔结构,包含微孔、介孔和大孔。
进一步的,所述相互连结氮/硫共掺杂多孔碳纳米片具有多级孔结构,氮元素与硫元素共同掺入到碳材料中,氮元素具有吡啶氮、吡咯氮和季胺氮三种状态,硫元素具有氧化态硫和噻吩硫二种状态。
本发明的有益效果:
制备方法简单,成本低廉。以掺杂甲基橙的聚吡咯纳米管为前驱体,通过在氮气气氛下进行简单的热处理,制备了相互连结的氮/硫共掺杂多孔碳纳米片。所制备的相互连结的氮/硫共掺杂多孔碳纳米片具有较高的比表面积和孔体积,以及包含微孔、介孔、大孔的多级孔结构。这些结构特征使所制备的相互连结的氮/硫共掺杂多孔碳纳米片作为量子点敏化太阳能电池用电极材料使用,具有优异的电化学性能。
附图说明
图1是本发明(对应实施例3)相互连结氮/硫共掺杂多孔碳纳米片的扫描电子显微镜照片;
图2是本发明(对应实施例3)相互连结氮/硫共掺杂多孔碳纳米片的透射电子显微镜照片;
图3是本发明(对应实施例3)相互连结氮/硫共掺杂多孔碳纳米片的高分辨透射电子显微镜照片;
图4是本发明(对应实施例3)相互连结氮/硫共掺杂多孔碳纳米片的氮吸附-脱附等温线;
图5是本发明(对应实施例3)相互连结氮/硫共掺杂多孔碳纳米片的孔尺寸分布曲线;
图6是本发明(对应实施例3)相互连结氮/硫共掺杂多孔碳纳米片的XPS扫描谱;
图7是本发明(对应实施例3)相互连结氮/硫共掺杂多孔碳纳米片的N1s拟合谱图;
图8是本发明(对应实施例3)相互连结氮/硫共掺杂多孔碳纳米片的S2p的拟合谱图;
图9是本发明(对应实施例3)相互连结氮/硫共掺杂多孔碳纳米片(NSPCNS)电极与传统PbS电极的Nyquist图;
图10是本发明(对应实施例3)相互连结氮/硫共掺杂多孔碳纳米片(NSPCNS)电极与传统PbS电极组装的量子点敏化太阳能电池的电流密度-电压曲线。
具体实施方式
实施例1
将0.35g的甲基橙(MO)和3g的FeCl3·6H2O溶于300mL去离子水中,然后将0.7g吡咯单体加入上述水溶液中,室温下搅拌18h,制备甲基橙(MO)掺杂的聚吡咯(PPy)纳米管;将合成的甲基橙掺杂的聚吡咯纳米管用去离子水和乙醇清洗;洗净后的甲基橙掺杂的聚吡咯纳米管在60℃真空烘箱中干燥;干燥后的甲基橙掺杂的聚吡咯纳米管3g与KOH 3g(按重量比1:1)混合均匀,然后将纳米管/KOH混合物放入马弗炉中,在N2保护下升温到800℃,热处理3h;升温速率为10℃/min;冷却到室温后,用1mol/L HCl和去离子水清洗,以除去无机盐杂质;清洗干净的样品在80℃真空烘箱中烘干,得到相互连结的氮/硫共掺杂多孔碳纳米片。
实施例2
将0.65g的甲基橙和6g的FeCl3·6H2O溶于300mL去离子水中,然后将1.4g吡咯单体加入上述水溶液中,室温下搅拌24h,制备MO掺杂的PPy纳米管;将合成的MO掺杂PPy纳米管用去离子水和乙醇清洗;洗净后的MO掺杂PPy纳米管在60℃真空烘箱中干燥;干燥后的MO掺杂PPy纳米管与KOH按重量比1:3混合均匀,然后将MO掺杂PPy纳米管/KOH混合物放入马弗炉中,在N2保护下升温到600℃,热处理1h;升温速率为3℃/min;冷却到室温后,用1M HCl和去离子水清洗,以除去无机盐杂质;清洗干净的样品在80℃真空烘箱中烘干;制备相互连结的氮/硫共掺杂多孔碳纳米片。
实施例3
将0.5g甲基橙(MO)和3.9g FeCl3·6H2O溶于300mL去离子水中,然后将1g吡咯单体加入上述水溶液中,室温下搅拌20h,制备MO掺杂的PPy纳米管;将合成的MO掺杂PPy纳米管用去离子水和乙醇清洗;洗净后的MO掺杂PPy纳米管在60℃真空烘箱中干燥;干燥后的MO掺杂PPy纳米管与KOH按重量比1:2混合均匀,然后将MO掺杂PPy纳米管/KOH混合物放入马弗炉中,在N2保护下升温到700℃,热处理2h;升温速率为5℃/min;冷却到室温后,用1M HCl和去离子水清洗,以除去无机盐杂质;清洗干净的样品在80℃真空烘箱中烘干,制备相互连结的氮/硫共掺杂多孔碳纳米片。该纳米片用扫描电子显微镜、透射电子显微镜、N2吸附、X-射线光电子能谱对样品进行分析表征如图1-8所示。图1和图2表明所制备的样品呈相互连结的纳米片结构,相互连结的纳米片形成多孔三维结构,图3可以看出纳米片是多孔结构。由图4中脱附曲线计算所制备样品的比表面积为1744.8m2/g,孔体积为1.01cm3/g。图5表明所制备样品具有多级孔结构,包含微孔、介孔和大孔。图6-图8表明所制备样品中含有碳、氮、硫、氧四种元素。氮元素有吡啶氮、吡咯氮和季胺氮三种状态,硫元素有氧化态硫和噻吩硫二种状态。这表明氮与硫共同掺入到碳材料中。
将实施例3制备的相互连结的氮/硫共掺杂多孔碳纳米片用于量子点敏化太阳能电池电极,并组装了量子点敏化太阳能电池。分析了氮/硫共掺杂多孔碳纳米片的电催化性能和所组装电池的光电性能。
将150mg NSPCNs样品与0.1mL TiCl4、0.1mL 30%Triton X-100及5mL正丁醇通过超声和研磨形成碳浆。用刮涂法将碳浆沉积到清洗干净的FTO导电玻璃表面,碳层厚度控制在7μm左右。然后将制备的碳电极在300℃下热处理30min,制备用于量子点敏化太阳能电池的碳对电极。为了比较,通过将Pb片放入1M S、1M Na2S和0.1M NaOH溶液中制备PbS电极。对称薄层电池的电化学阻抗谱(EIS)分析氮/硫共掺杂多孔碳纳米片电极对多硫(S2-/Sn 2-)电解质再生反应的电催化活性。图9表明氮/硫共掺杂多孔碳纳米片电极对多硫(S2-/Sn 2-)电解质再生反应的电催化活性与传统的PbS电极相似。
量子点敏化太阳能电池光阳极的制备方法如下:将9μm厚TiO2(P25)膜沉积到FTO导电玻璃表面,450℃下处理30min。将TiO2电极交替浸入0.1M Cd(CH3COO)2溶液和0.1MNa2S溶液中各1min,重复6次,制备CdS-TiO2电极。4℃条件下,将CdS-TiO2电极浸入0.08MCdSO4、0.16M N(CH3COONa)3和0.08M Na2SeSO3混合溶液中20h,制备CdS/CdSe量子点共敏化TiO2电极。将CdS/CdSe量子点共敏化TiO2电极与对电极面对面夹一起,中间用60μm Surlyn膜隔离。两电极间空隙填充多硫电解质(S2-/Sn 2-)组装量子点敏化太阳能电池。用Keithley2400数字源表记录电池的光电性能。电池光电性能在100mW/cm2(AM1.5)模拟光照下测量。图10表明氮/硫共掺杂多孔碳纳米片对电极组装的量子点敏化太阳能电池光电效率为5.31%,与传统的PbS对电极电池(5.51%)几乎相同,而明显高于普通多孔碳材料对电极电池,是理想的量子点敏化太阳能电池电极材料。
以上仅为本发明的具体实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (5)
1.一种量子点敏化太阳能电池用对电极材料的制备方法,其特征是:
具体步骤是:
(1)制备掺杂甲基橙的聚吡咯纳米管
按照重量分数计,将0.35份-0.65份的甲基橙(MO)和3份-6份的FeCl3×6H2O溶于去离子水中,得到甲基橙-氯化铁混合水溶液;然后将0.7份-1.4份吡咯单体加入甲基橙-氯化铁混合水溶液中,室温下搅拌18h-24h,得到掺杂甲基橙的聚吡咯(PPy)纳米管;
(2)将掺杂甲基橙的聚吡咯纳米管用去离子水和乙醇清洗后,在60℃真空烘箱中干燥,干燥后的掺杂甲基橙的聚吡咯纳米管与KOH按照重量比1:1-1:3混合均匀,得到纳米管/KOH混合物;然后将纳米管/KOH混合物在N2保护下升温到600℃-800℃,热处理1h-3h,冷却到室温后,用1mol/L HCl和去离子水清洗杂质;然后在80℃真空烘箱中烘干,得到相互连结氮/硫共掺杂多孔碳纳米片。
2.根据权利要求1所述的量子点敏化太阳能电池用对电极材料的制备方法,其特征是:步骤(1)中所述FeCl3×6H2O与去离子水的质量体积比为0.01g/mL-0.02g/mL。
3.根据权利要求1所述的量子点敏化太阳能电池用对电极材料的制备方法,其特征是:热处理时,升温速率为3℃/min-10℃/min。
4.根据权利要求1所述的量子点敏化太阳能电池用对电极材料的制备方法,其特征是:所述相互连结氮/硫共掺杂多孔碳纳米片具有多级孔结构,包含微孔、介孔和大孔。
5.根据权利要求1所述的量子点敏化太阳能电池用对电极材料的制备方法,其特征是:所述相互连结氮/硫共掺杂多孔碳纳米片具有多级孔结构,氮元素与硫元素共同掺入到碳材料中,氮元素具有吡啶氮、吡咯氮和季胺氮三种状态,硫元素具有氧化态硫和噻吩硫二种状态。
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