CN106847364A - 一种铜锌锡硫和三维石墨烯的复合薄膜的制备方法及应用 - Google Patents
一种铜锌锡硫和三维石墨烯的复合薄膜的制备方法及应用 Download PDFInfo
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Abstract
本发明涉及一种铜锌锡硫和三维石墨烯的复合薄膜的制备方法及应用，其特征在于：采用溶剂热合成技术，在三维多孔结构的石墨烯薄膜表面及其多孔空间内生长铜锌锡硫纳米材料，制备出铜锌锡硫纳米颗粒和三维石墨烯的复合薄膜。经过形貌和电化学的测量实验表明，这种铜锌锡硫和三维石墨烯复合薄膜具有高比表面积、高导电性和高催化特性，作为染料敏化太阳能电池的光阳极材料。
Description
技术领域
本发明涉及的是一种纳米材料技术领域的方法，具体铜锌锡硫和三维石墨烯的复合薄膜的制备方法及应用。
背景技术
纳米复合材料可以集中单独材料的优良性能，基于这一思路的基础上，通过合理设计材料的结构与形貌对于纳米材料的性能和应用具有重要影响，更重要的是纳米材料的均匀分布对于其在能源环境如太阳能电池、光催化、超级电容器等领域有重要意义，因此纳米复合材料的控制和合成愈来愈受到重视。
铜锌锡硫(缩写作CZTS)纳米颗粒具有很多优点，比如：光吸收系数超过104cm-1，带隙大约是1.5eV，铜、锌、锡、硫元素在自然界储量丰富，不污染环境。目前它应用于太阳能电池的效率已经超过了10％。对于铜锌锡硫纳米颗粒的制备，通常采用热注射法。但是，这些方法用的化学试剂比较刺激或者是要用长链表面活性剂。另外就是使用溶剂热法，常用表面活性剂聚乙烯吡咯烷酮(PVP)来控制纳米颗粒的大小和形貌。当应用于光伏或者光电催化薄膜时，表面活性剂吸附在颗粒表面，某种程度上阻碍了颗粒之间的电子传输。在扩大生产的时候，表面活性剂的使用也会引发环境问题。
铜锌锡硫CZTS)是直接带隙p型半导体，禁带宽度为1.5eV左右,吸收系数高达104cm-1，并且CZTS薄膜制备方法简单，组成元素在地球上储量丰富，价格低且无毒性，因此被人们认为具有极大的发展前景。石墨烯是超薄二维纳米材料，具有电子流动性强200000cm2V-1s-1)，机械性能和稳定性能好等优良特性。
经过对现有技术的检索发现，中国专利文献号103219066A，公开了一种二维石墨烯与一维纳米线复合的柔性导电薄膜及其制备方法。该技术将石墨烯、纳米线与分散助剂分散到溶剂中，超声震荡，得到分散良好的石墨烯/纳米线溶液，经真空抽滤、干燥后，得到石墨烯/纳米线复合薄膜。所述复合薄膜厚度为10nm-1000μm，有良好的强度和柔性，方块电阻在0.001-3000Ω/sq.范围内，电导率为0.01-5000S/cm。但该技术仅涉及了纳米线和石墨烯的复合物，且制备过程较为复杂，同时复合薄膜无法达到量子点级别。
基于此，本发明提出了一种改进的铜锌锡硫纳米颗粒和三维石墨烯的复合薄膜的制备方法。
发明内容
针对现有技术存在的不足，本发明采用溶剂热合成技术，在三维多孔结构的石墨烯薄膜表面及其多孔空间内生长铜锌锡硫纳米材料，制备出铜锌锡硫纳米颗粒和三维石墨烯的复合薄膜。经过形貌和电化学的测量实验表明，这种铜锌锡硫和三维石墨烯复合薄膜具有高比表面积、高导电性和高催化特性，可作为染料敏化太阳能电池的光阳极材料。
本发明涉及的技术方案如下：
一种铜锌锡硫和三维石墨烯的复合薄膜的制备方法，包括以下步骤：
步骤一、在导电基底上制备出三维石墨烯薄膜：
首先，基于超声改进的Hummer法制备出氧化石墨烯，在马弗炉中利用200-1000℃高温还原。将氧化还原石墨烯粉末与乙醇溶液的混合物进行球磨处理。最后将球磨后的石墨烯分散溶液抽滤烘干，得到单层石墨烯粉末。
其次，将球磨处理后的单层石墨烯粉末加入到有机溶剂中，配制成石墨烯浆料，利用丝网印刷在FTO导电玻璃的导电面上。
最后，将上述样品置于鼓风干燥箱进行热处理后，得到基于导电基底的三维多孔石墨烯薄膜待用。
步骤二、制备铜锌锡硫/三维石墨烯复合薄膜：
首先，将上述制备的基于导电基底的三维石墨烯薄膜倾斜置于高压反应釜内衬中，加入以乙醇为溶剂，以聚乙烯吡咯烷酮为活性剂，以氯化铜、氯化锌、氯化亚锡和硫脲作为反应剂的金属硫化物前驱液，然后封釜，进行高温水热反应。
其次，将反应后的样品取出，去离子水清洗后干燥，得到铜锌锡硫/三维石墨烯复合薄膜。
进一步地，所述石墨烯浆料的制备为：0.9g乙基纤维素加入到8.1g的无水乙醇中，搅拌均匀后再加入9g松油醇和9g无水乙醇。最后加入准备好的0.05-0.1g单层石墨烯粉末。磁力搅拌20min，再超声分散20min,交替3-5次。然后再搅拌蒸发干无水乙醇。再加入0.6ml乙酰丙酮和0.6ml OP乳化剂搅拌均匀后得到石墨烯浆料。
所述高温水热反应为：1)称取2mmol氯化锌、0.5mmol氯化亚锡、1mmol氯化铜和0.25mmol聚乙烯吡咯烷酮溶解在40ml乙醇溶剂中，磁力搅拌至充分溶解成，再加入10mmol硫脲，搅拌至澄清无色。2)将所配置溶液倒入60ml反应釜，倾斜放入基于导电基底的三维多孔石墨烯薄膜。3)放置鼓风干燥箱，180℃-210℃下恒温反应12-24h。
附图说明
图1为三维石墨烯薄膜截面的SEM图
图2为铜锌锡硫三维石墨烯复合薄膜截面的SEM图
图3为三维石墨烯薄膜表面的SEM图
图4铜锌锡硫三维石墨烯复合薄膜表面的SEM图
具体实施方式
步骤一、在导电基底上制备出三维石墨烯薄膜：
首先，基于超声改进的Hummer法制备出氧化石墨烯，在马弗炉中利用200-1000℃高温还原。将氧化还原石墨烯粉末与乙醇溶液的混合物进行球磨处理。氧化钴球磨珠与氧化还原石墨烯粉末的球料质量比约为10000:1至2000:1,转速为200-400转/分钟，球磨时间10-30h。最后将球磨后的石墨烯分散溶液抽滤烘干，得到单层石墨烯粉末。
其次，将球磨处理后的单层石墨烯粉末加入到有机溶剂中，配制成石墨烯浆料，利用丝网印刷在FTO导电玻璃的导电面上。
最后，将上述样品置于鼓风干燥箱进行热处理后，得到基于导电基底的三维多孔石墨烯薄膜待用。
1.石墨烯浆料的制备：0.9g乙基纤维素加入到8.1g的无水乙醇中，搅拌均匀后再加入9g松油醇和9g无水乙醇。最后加入准备好的0.05-0.1g单层石墨烯粉末。磁力搅拌20min，再超声分散20min,交替3-5次。然后再搅拌蒸发干无水乙醇。再加入0.6ml乙酰丙酮和0.6ml OP乳化剂搅拌均匀后得到石墨烯浆料。
2.采用溶剂热合成技术，以乙醇为溶剂，以聚乙烯吡咯烷酮为活性剂，以氯化铜、氯化锌、氯化亚锡和硫脲作为反应剂。1)称取2mmol氯化锌、0.5mmol氯化亚锡、1mmol氯化铜和0.25mmol聚乙烯吡咯烷酮溶解在40ml乙醇溶剂中，磁力搅拌至充分溶解成，再加入10mmol硫脲，搅拌至澄清无色。2)将所配置溶液倒入60ml反应釜，倾斜放入基于导电基底的三维多孔石墨烯薄膜。3)放置鼓风干燥箱，180℃-210℃下恒温反应12-24h。
如图1-4所示，经过热处理后的三维石墨烯形成了互联结构，与基底有很好接触并且薄膜内部具有很大的空隙。这种在衬底上制备的三维石墨烯薄膜结构还没见报道。而且这种三维石墨烯薄膜有很高的透过率。在FTO导电玻璃上印刷不同层数浆料，热处理后的三维石墨烯薄膜具有不同厚度和透过率，50纳米厚的三维石墨烯薄膜在可见光范围内的550nm波长有约为90％的透过率，经计算随着厚度增加，每纳米有0.08％的透过率衰减。这种高透过率得益于三维石墨烯薄膜的三维多孔中空结构。
在三维石墨烯薄膜表面和内部都生长了均匀分布的CZTS花状纳米颗粒，大小约为200nm。生长了纳米材料之后的薄膜厚度没有明显变化，依然保持三维多孔结构，这对作为太阳能电池对电极是很有帮助的。因为，更多的电解液可以渗透到电极内部，与催化纳米材料有更高的接触面积，而且维持原有的导电网络，加快了电子的传输速度。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。
Claims (5)
1.一种铜锌锡硫和三维石墨烯的复合薄膜的制备方法，其特征在于，包括以下步骤：
步骤一、在导电基底上制备出三维石墨烯薄膜：
首先，基于超声改进的Hummer法制备出氧化石墨烯，在马弗炉中利用200-1000℃高温还原，将氧化还原石墨烯粉末与乙醇溶液的混合物进行球磨处理，最后将球磨后的石墨烯分散溶液抽滤烘干，得到单层石墨烯粉末；
其次，将球磨处理后的单层石墨烯粉末加入到有机溶剂中，配制成石墨烯浆料，利用丝网印刷在FTO导电玻璃的导电面上；
最后，将上述样品置于鼓风干燥箱进行热处理后，得到基于导电基底的三维多孔石墨烯薄膜待用；
步骤二、制备铜锌锡硫/三维石墨烯复合薄膜：
首先，将上述制备的基于导电基底的三维石墨烯薄膜倾斜置于高压反应釜内衬中，加入以乙醇为溶剂，以聚乙烯吡咯烷酮为活性剂，以氯化铜、氯化锌、氯化亚锡和硫脲作为反应剂的金属硫化物前驱液，然后封釜，进行高温水热反应；
其次，将反应后的样品取出，去离子水清洗后干燥，得到铜锌锡硫/三维石墨烯复合薄膜。
2.如权利要求1所述的一种铜锌锡硫和三维石墨烯的复合薄膜的制备方法，其特征在于，所述球磨时采用氧化钴球磨珠与氧化还原石墨烯粉末的球料质量比约为10000:1至2000:1,转速为200-400转/分钟，球磨时间10-30h。
3.如权利要求2所述的一种铜锌锡硫和三维石墨烯的复合薄膜的制备方法，其特征在于，所述石墨烯浆料的制备为：0.9g乙基纤维素加入到8.1g的无水乙醇中，搅拌均匀后再加入9g松油醇和9g无水乙醇，最后加入准备好的0.05-0.1g单层石墨烯粉末，磁力搅拌20min，再超声分散20min,交替3-5次，然后再搅拌蒸发干无水乙醇，再加入0.6ml乙酰丙酮和0.6mlOP乳化剂搅拌均匀后得到石墨烯浆料。
4.如权利要求3所述的一种铜锌锡硫和三维石墨烯的复合薄膜的制备方法，其特征在于，所述高温水热反应为：1)称取2mmol氯化锌、0.5mmol氯化亚锡、1mmol氯化铜和0.25mmol聚乙烯吡咯烷酮溶解在40ml乙醇溶剂中，磁力搅拌至充分溶解成，再加入10mmol硫脲，搅拌至澄清无色，2)将所配置溶液倒入60ml反应釜，倾斜放入基于导电基底的三维多孔石墨烯薄膜，3)放置鼓风干燥箱，180℃-210℃下恒温反应12-24h。
5.如权利要求1-4任一项所述的一种铜锌锡硫和三维石墨烯的复合薄膜的制备方法制备得到的复合薄膜。
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| CN109678358A (zh) * | 2018-12-13 | 2019-04-26 | 广东工业大学 | 一种在导电玻璃衬底上制备碳纳米管的方法 |
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| CN109678358A (zh) * | 2018-12-13 | 2019-04-26 | 广东工业大学 | 一种在导电玻璃衬底上制备碳纳米管的方法 |
| CN109830549A (zh) * | 2018-12-13 | 2019-05-31 | 广东工业大学 | 一种硫化铟/石墨烯复合薄膜及其制备方法和应用 |
| CN112225244A (zh) * | 2020-10-13 | 2021-01-15 | 江曙 | 一种太阳能电池用单分散纳米铜锌锡硫的制备方法 |
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