CN102290477B - 一种基于石墨烯pn结的光伏电池及其制备方法 - Google Patents
一种基于石墨烯pn结的光伏电池及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种基于石墨烯PN结的光伏电池及其制备方法。光伏电池是由基底、透明导电薄膜、P型石墨烯薄膜和N型石墨烯薄膜形成的PN结以及对电极构成。将基底和透明导电膜清洗,N2吹干备用;分别制备硼掺杂石墨烯和氮掺杂石墨烯;将制得的两种石墨烯分别溶于水合胆酸钠,配制石墨烯溶液;将氮掺杂石墨烯溶液经混合纤维素滤膜抽滤,滴入去离子水,在氮掺杂石墨烯薄膜表面缓慢滴加硼掺杂石墨烯溶液抽滤成膜,将得到的薄膜倒置于备用的基底表面,压实,采用丙酮蒸馏,并在室温条件下依次经丙酮和甲醇浸泡清洗;将对电极覆盖于薄膜表面压制形成石墨烯PN结光伏电池。该方法制备和组装工艺简单,成本低廉,适于规模化应用,促进了石墨烯在太阳能电池方面的应用。
Description
技术领域:
本发明涉及一种以P型石墨烯和N型石墨烯构成PN结为基础构建的光伏电池及其制备方法,属于石墨烯基太阳能电池技术领域。
背景技术:
当今社会,能源危机和环境恶化问题日益突出,太阳能作为一种清洁、可再生能源得到人们的广泛关注。光伏电池是太阳能利用的主要形式之一,其使用对缓解石化能源所带来的环境污染及因其日益枯竭所带来的能源危机具有重要意义。目前,广泛使用的是硅太阳能电池。但是,传统的硅太阳能电池具有制备工艺复杂、高能耗、废料、噪音、污染等问题,因而限制了其进一步发展。因此,寻找硅的替代材料或减少硅的使用率是目前的研究热点。
自2004年Novoselov和Geim等人[Science,2004,306,666.]制备出碳原子以SP2杂化连接的新型二维原子晶体石墨烯之后,其独特的理化性质立即引起物理、化学、材料等不同领域科学家的广泛关注,使其成为各领域的研究热点。石墨烯即为单层石墨片,是由一层密集的、包裹在蜂窝状晶体点阵上的碳原子组成的二维材料。它可以翘曲成零维的富勒烯,卷成一维的碳纳米管或堆垛成三维的石墨,是构成其他石墨材料的基本单元。石墨烯具有六角平面网状结构,六角平面内三个sp2杂化轨道互成120°角排列,与相邻碳原子形成共价键。每个碳原子与另外三个碳原子相连,六个碳原子在同一平面上形成正六边形的环,伸展形成片层结构。在同一平面的碳原子还各剩下一个p轨道,它们互相重叠,形成离域的π键电子在晶格中能自由移动,可以被激发。因此,石墨烯具有独特的理化性质,如比表面积高、热导性高、机械强度高、力学性能好、电子迁移率高等,可以制备出多种柔性电子器件和功能复合材料,在能源、材料、电子信息和生物医药领域都具有重大的应用前景。
研究发现[l.Dong,et al.Carbon 2010,48,781],石墨烯可显著提高Pt和Pt-Ru纳米粒子的电催化活性。碳纳米管PN结(N.M.Gabor,et al.Science 2009,325,1367)、碳纳米管/硅异质结(专利号:200610169827.0;Y Jia,et al.Adv.Mater.2008,20,4594)、石墨烯/硅异质结(专利号:200910219530.4)均显示出一定的光伏效应。然而,目前对碳纳米管的手性尚无法进行精确控制,难以制备出光伏性能可控的碳纳米管宏观结构。
发明内容:
本发明的目的在于克服现有技术的缺点,提供一种可完全替代硅材料的基于石墨烯PN结的光伏电池及其制备方法。以P型石墨烯和N型石墨烯构成的PN结为基础构建光伏电池,充 分利用石墨烯薄膜优异的透光性、导电性和光伏性制备太阳能电池。该方法制备和组装工艺简单,成本低,适于规模化应用。
为了实现上述发明目的,本发明的光伏电池是由基底、透明导电薄膜、P型石墨烯薄膜和N型石墨烯薄膜形成的PN结以及对电极构成。
其中,所述基底为硅、玻璃、塑料、橡胶、金属、陶瓷等;透明导电薄膜为石墨烯、单壁碳纳米管、多壁碳纳米管、ITO导电玻璃、FTO导电玻璃、导电高分子、导电陶瓷等材料;对电极为石墨烯、单壁碳纳米管、多壁碳纳米管、导电高分子、导电陶瓷、金、铂金、钯、铝、铜、铬等金属及合金材料等。
所述P型石墨烯是由硼等III族元素掺杂的石墨烯材料;N型石墨烯是由氮、磷等V族元素掺杂的石墨烯材料。
一种基于石墨烯PN结的光伏电池的制备方法,按照以下步骤操作:
(1)将基底和透明导电膜依次经丙酮、乙醇和去离子水分别超声清洗,N2吹干备用;
(2)分别制备硼掺杂石墨烯和氮掺杂石墨烯;
(3)将制得的两种石墨烯分别溶于水合胆酸钠(2mg∶1mL),配制石墨烯溶液;
(4)将氮掺杂石墨烯溶液经混合纤维素滤膜抽滤,滴入去离子水,采用相同的工艺,在氮掺杂石墨烯薄膜表面缓慢滴加硼掺杂石墨烯溶液抽滤成膜,将得到的薄膜倒置于备用的基底表面,压实,采用丙酮蒸馏,并在室温条件下依次经丙酮和甲醇浸泡清洗;
(5)将1-2g氯铂酸(H2PtCl6)溶于100-200mL异丙醇中,得到氯铂酸异丙醇溶液,通过旋涂法涂覆于清洗干净的基底表面,在300-400℃热处理15-20min得到对电极;或采用真空溅射法在FTO玻璃或ITO玻璃表面沉积金薄膜得到对电极;
(6)将对电极覆盖于(4)得到的薄膜表面压制形成石墨烯PN结光伏电池。
其中,透明导电薄膜的制备:a、ITO或FTO导电玻璃可作为透明导电薄膜使用;b、采用旋涂或者刮涂工艺在洗净的硅、玻璃、塑料、橡胶、金属、陶瓷等基底表面制作石墨烯、单壁碳纳米管、多壁碳纳米管、导电高分子、导电陶瓷等薄膜。
硼掺杂石墨烯制备方法为:取2-10mL CCl4置于反应釜中,将25-50μmL溴化硼(BBr3)注入CCl4,并加入0.5-2g钾作为催化剂,控制反应温度为160-210℃,时间为30min-10h;将所得产物溶于丙酮,强力搅拌后离心,所得产物加入1L去离子水中,强力搅拌后抽滤(期间用1L去离子水冲洗),该过程重复两遍;抽滤结束后烘干,得到硼掺杂石墨烯。
氮掺杂石墨烯制备方法为:取2-20mL CCl4置于反应釜中,加入0.5-2g氮化锂(Li3N),控制反应温度为200-250℃,时间为2-10h;将产物溶于丙酮,强力搅拌后离心,所得产物置于18wt.%HCl溶液中,强力搅拌后抽滤,然后用去离子水清洗,并将所得产物烘干,得 到氮掺杂石墨烯。
本发明方法操作简单,成本低廉,促进了石墨烯在太阳能电池方面的应用。
附图说明:
图1是基于石墨烯PN结光伏电池的结构示意图。
图2是氮掺杂石墨烯的透射电子显微镜形貌图。
图3是纯石墨烯Graphene、氮掺杂N-6raphene和硼掺杂B-Graphene石墨烯的拉曼谱图。
具体实施方式:
下面通过具体实施例对本发明做进一步阐述。
一种基于石墨烯PN结的光伏电池,以FTO或ITO玻璃为基底1和透明导电薄膜2,在其表面通过刮涂法、喷涂法、丝网印刷法、电泳法、甩胶法、刷涂法、旋涂法或提拉法等依次制备硼掺杂的P型石墨烯薄膜3和氮掺杂的N型石墨烯薄膜4构成PN结,然后覆盖涂覆铂的FTO玻璃为对电极5,形成PN结光伏电池,其结构见图1。
实施例1:一种基于石墨烯PN结的光伏电池的制备方法,按照以下步骤操作:
(1)FTO玻璃或ITO玻璃为基底1和透明导电薄膜2,依次经丙酮、乙醇和去离子水分别超声清洗15min,N2吹干备用;
(2)取10mL CCl4置于50ml反应釜中,将50μmL溴化硼(BBr3)注入CCl4,并加入0.5g钾作为催化剂,控制反应温度为160℃,时间为2h,将所得产物溶于丙酮,强力搅拌1h后离心,所得产物加入1L去离子水中,强力搅拌1h后抽滤(期间用1L去离子水冲洗),该过程重复两遍;抽滤结束后在真空干燥箱内烘干,得到硼掺杂石墨烯3;
(3)取15mL CCl4置于50ml反应釜中,加入0.5g氮化锂,控制反应温度为200℃,时间为2h,将产物溶于丙酮,强力搅拌1h后离心,所得产物置于18wt.%HCl溶液中,强力搅拌1h后抽滤,然后用去离子水清洗,并将所得产物置于真空干燥箱内烘干,得到氮掺杂石墨烯4(其透射电子显微镜形貌图见图2);
纯石墨烯Graphene、氮掺杂N-Graphene和硼掺杂B-Graphene石墨烯的拉曼谱图见图3,由图可知,掺杂石墨烯与石墨烯谱图存在差异,表明硼和氮的掺杂可有效改变石墨烯的晶体结构以及其电性能。
(4)将得到的两种石墨烯分别溶于水合胆酸钠(2mg∶1mL),配制石墨烯溶液;
(5)将氮掺杂石墨烯溶液经孔径为800nm的混合纤维素滤膜抽滤10min,滴入20mL去离子水,采用相同的工艺,在氮掺杂石墨烯薄膜表面缓慢滴加硼掺杂石墨烯溶液抽滤成膜,将得到的薄膜倒置于(1)中备好的玻璃表面,压实,采用丙酮蒸馏2h,并在室温条件下依次经丙酮和甲醇浸泡清洗;
(6)将1g氯铂酸(H2PtCl6)溶于100mL异丙醇中,得到氯铂酸异丙醇溶液,通过旋涂法涂覆于清洗干净的FTO玻璃或ITO玻璃表面,经400℃热处理15min得到对电极5;
(7)将对电极5覆盖于(5)得到的薄膜表面压制形成石墨烯PN结光伏电池。
实施例2:一种基于石墨烯PN结的光伏电池的制备方法,按照以下步骤操作:
(1)FTO玻璃或ITO玻璃为基底1和透明导电薄膜2,依次经丙酮、乙醇和去离子水分别超声清洗15min,N2吹干备用;
(2)取5mL CCl4置于50ml反应釜中,将50μmL溴化硼(BBr3)注入CCl4,并加入1g钾作为催化剂,控制反应温度为160℃,时间为2h,将所得产物溶于丙酮,强力搅拌1h后离心,所得产物加入1L去离子水中,强力搅拌1h后抽滤(期间用1L去离子水冲洗),该过程重复两遍。抽滤结束后在真空干燥箱内烘干,得到硼掺杂石墨烯3;
(3)取5mL CCl4置于50ml反应釜中,加入1g氮化锂,控制反应温度为240℃,时间为2h,将产物溶于丙酮,强力搅拌1h后离心,所得产物置于18wt.%HCl溶液中,强力搅拌1h后抽滤,然后用去离子水清洗,并将所得产物置于100℃烘箱,干燥12h,得到氮掺杂石墨烯4;
(4)将得到的两种石墨烯分别溶于水合胆酸钠(2mg∶1mL),配制石墨烯溶液;
(5)将氮掺杂石墨烯溶液经孔径为800nm的混合纤维素滤膜抽滤10min,滴入25mL去离子水,采用相同的工艺,在氮掺杂石墨烯薄膜表面缓慢滴加硼掺杂石墨烯溶液抽滤成膜,将得到的薄膜倒置于(1)中备好的玻璃表面,压实,采用丙酮蒸馏2h,并在室温条件下依次经丙酮和甲醇浸泡清洗;
(6)采用真空溅射法在清新干净的FTO玻璃或ITO玻璃表面沉积金薄膜,得到对电极5;
(7)将对电极5覆盖于(5)得到的薄膜表面压制形成石墨烯PN结光伏电池。
Claims (4)
1.一种基于石墨烯PN结的光伏电池制备方法,其特征在于按照以下步骤操作:第一步,将基底和透明导电膜依次经丙酮、乙醇和去离子水分别超声清洗,N2吹干备用;第二步,分别制备硼掺杂石墨烯和氮掺杂石墨烯;第三步,将制得的两种石墨烯按照2mg:1mL的比例分别溶于水合胆酸钠,配制石墨烯溶液;第四步,将氮掺杂石墨烯溶液经混合纤维素滤膜抽滤,滴入去离子水,采用相同的工艺,在氮掺杂石墨烯薄膜表面缓慢滴加硼掺杂石墨烯抽滤成膜,将得到的薄膜倒置于备用的基底表面,压实,采用丙酮蒸馏,并在室温条件下依次经丙酮和甲醇浸泡清洗;第五步,将1-2g氯铂酸溶于100-200mL异丙醇中,得到氯铂酸异丙醇溶液,通过旋涂法涂覆于清洗干净的基底表面,在300-400℃热处理15-20min得到对电极;或采用真空溅射法在FTO玻璃或ITO玻璃表面沉积金薄膜得到对电极;第六步,将对电极覆盖于第四步得到的薄膜表面压制形成石墨烯PN结光伏电池。
2.根据权利要求1所述的基于石墨烯PN结的光伏电池制备方法,其特征在于透明导电膜的制备:ITO或FTO导电玻璃作为透明导电薄膜使用;或采用旋涂或者刮涂工艺在洗净的硅、玻璃、塑料、橡胶、金属、陶瓷基底表面制作石墨烯、单壁碳纳米管、多壁碳纳米管、导电高分子、导电陶瓷薄膜。
3.根据权利要求1所述的基于石墨烯PN结的光伏电池制备方法,其特征在于硼掺杂石墨烯制备为:取2-10mL CCl4置于反应釜中,将25-50μmL溴化硼注入CCl4,并加入0.5-2g钾作为催化剂,控制反应温度为160-210℃,时间为30min-10h;将所得产物溶于丙酮,强力搅拌后离心,所得产物加入1L去离子水中,强力搅拌后抽滤,期间用1L去离子水冲洗,该过程重复两遍;抽滤结束后烘干,得到硼掺杂石墨烯。
4.根据权利要求1所述的基于石墨烯PN结的光伏电池制备方法,其特征在于氮掺杂石墨烯制备为:取2-20mL CCl4置于反应釜中,加入0.5-2g氮化锂,控制反应温度为200-250℃,时间为2-10h;将产物溶于丙酮,强力搅拌后离心,所得产物置于18wt.%HCl溶液中,强力搅拌后抽滤,然后用去离子水清洗,并将所得产物烘干,得到氮掺杂石墨烯。
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