CN106971771A - 一种碳包覆金属纳米线导电薄膜的制备方法 - Google Patents
一种碳包覆金属纳米线导电薄膜的制备方法 Download PDFInfo
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Abstract
本发明公开了一种碳包覆金属纳米线导电薄膜的制备方法。将一定量的金属纳米线分散于葡萄糖溶液中,在160‑200℃条件下水热反应1‑5小时即可。所述金属纳米线为金、银、铜等金属纳米线或其合金及混合物。所述金属纳米线透明导电薄膜可以通过喷涂或者薄膜转移法制得。所述方法简单易行,可以显著提高金属纳米线导电薄膜的稳定性。本方法有望促进金属纳米线透明导电薄膜在太阳能电池等光电子器件领域的应用。
Description
技术领域
本发明属于太阳能电池技术领域,尤其涉及一种碳包覆金属纳米线导电薄膜的制备方法。
背景技术
透明导电电极是太阳能电池等新型光电子器件的重要部件。以氧化铟锡(ITO)及氟掺杂氧化锡(FTO)为代表的透明导电氧化物 (TCO) 材料是目前最常用的透明导电电极材料。TCO材料具有成本高,柔韧性差等缺点。为此,有必要寻求更为廉价且兼具柔性的高性能透明导电电极材料。
近年来,基于银、铜等金属纳米线的透明导电薄膜引起了广泛的研究,它们具有良好的导电性、透光性和柔性,且制备简单、成本低廉。然而银、铜等金属纳米线的化学性质较为活泼,易被空气氧化或者化学物质腐蚀,进而严重损害薄膜的导电性,这是金属纳米线透明导电薄膜实际应用的主要障碍。在金属纳米线透明导电薄膜表面覆以惰性的保护层(如聚合物或金属氧化物薄膜)可以增强其抗氧化及抗腐蚀性能,然而这类方法并不能从根本上改善金属纳米线的稳定性,且其局限性也显而易见:若保护层太薄则不能起到有效的保护作用;若保护层太厚则会损害薄膜的导电性和透光性。我们知道,碳材料具有极好的稳定性和相当的导电性能,倘若利用碳材料对金属纳米线进行原位包覆,则有望在不损害薄膜导电性及透光性的情况下,从根本上改善金属纳米线导电薄膜的稳定性。
发明内容
本发明所要解决的技术问题在于提供一种碳包覆金属纳米线导电薄膜的制备方法,该方法可以增强金属纳米线抗氧化、抗腐蚀性能,使其可以用于制备高性能透明导电薄膜,应用于太阳能电池等光电子器件。
本发明的一种碳包覆金属纳米线导电薄膜的制备方法,包含以下步骤:
(1)配制异丙醇和水的混合溶液,其中异丙醇和水的体积比为1-2,再往溶液中加入0.03-0.2g/ml量的葡萄糖;
(2)往(1)溶液中加入一定量的金属纳米线,金属纳米线和葡萄糖的摩尔比为0.01-0.1;
(3)将(2)溶液按50%的体积比填充度置于反应釜中,在160-200℃下反应1-5小时;
(4)离心,清洗,再分散;
(5)利用(4)制备的碳包覆金属纳米线通过喷涂或膜转移方法制备透明导电薄膜。
所述的金属纳米线为金纳米线、银纳米线、铜纳米线中的一种或几种,或为金、银、铜合金的纳米线。所述金属纳米线均可根据本领域公知技术得到。
本发明选择低成本且易于制备的铜纳米线(CuNWs)作为实施例,铜纳米线的制备方法如下:
将50mg 二水氯化亚铜,300 十六胺,150mg 葡萄糖溶于20ml 的去离子水中,100摄氏度加热反应6小时生成铜纳米线,提纯后分散于异丙醇中得到铜纳米线分散液。
本发明的的优点在于:操作简单,能有效的在金属纳米线薄膜包覆均匀的碳膜且碳膜厚度可控、不影响金属纳米线的导电性,可以显著提高金属纳米线透明导电薄膜的稳定性。
附图说明
图1为本发明中制备的铜纳米线SEM图。
图2a-f分别为实施例1-6所制备的碳包覆铜纳米线 (CuNWs@C)的TEM图。
图3为实施例3所制备碳包覆纳米线导电薄膜和铜纳米线导电薄膜在空气中导电性变化的对比图。
图4为基于实施例3所制备碳包覆纳米线导电薄膜导电薄膜和FTO所制备的对电极在染料敏化太阳电池应用中的性能图。
具体实施方式
以下通过一些具体实施例来更详细的说明本发明,但本发明并不限定于这些实施例。
下列实施例中使用的铜纳米线的制备方法如下:
将50mg 二水氯化亚铜,300 十六胺,150mg 葡萄糖溶于20ml 的去离子水中,100摄氏度加热反应6小时生成铜纳米线,提纯后分散于异丙醇中得到铜纳米线分散液。
实施例1
(1)配制15ml异丙醇和水的混合溶液,其中异丙醇和水的体积比为2,再往溶液中加入0.5g的葡萄糖。
(2)往(1)溶液中加入18.75 mg的铜纳米线。
(3)将(2)溶液置于30ml的水热反应釜中,在170℃下反应3小时。
(4)离心,清洗。
实施例2
(1)配制15ml异丙醇和水的混合溶液,其中异丙醇和水的体积比为1,再往溶液中加入1.5g的葡萄糖。
(2)往(1)溶液中加入18.75mg的铜纳米线。
(3)将(2)溶液置于30ml的水热反应釜中,在170℃下反应3小时。
(4)离心,清洗。
实施例3
(1)配制15ml异丙醇和水的混合溶液,其中异丙醇和水的体积比为2,再往溶液中加入1.5g的葡萄糖。
(2)往(1)溶液中加入18.75 mg的铜纳米线。
(3)将(2)溶液置于30ml的水热反应釜中,在170℃下反应3小时。
(4)离心,清洗。
实施例4
(1)配制15ml异丙醇和水的混合溶液,其中异丙醇和水的体积比为2,再往溶液中加入3g的葡萄糖。
(2)往(1)溶液中加入18.75 mg的铜纳米线。
(3)将(2)溶液置于30ml的水热反应釜中,在170℃下反应3小时。
(4)离心,清洗。
实施例5
(1)配制15ml异丙醇和水的混合溶液,其中异丙醇和水的体积比为2,再往溶液中加入1.5g的葡萄糖。
(2)往(1)溶液中加入18.75 mg的铜纳米线。
(3)将(2)溶液置于30ml的水热反应釜中,在170℃下反应1小时。
(4)离心,清洗。
实施例6
(1)配制15ml异丙醇和水的混合溶液,其中异丙醇和水的体积比为2,再往溶液中加入1.5g的葡萄糖。
(2)往(1)溶液中加入18.75 mg的铜纳米线。
(3)将(2)溶液置于30ml的水热反应釜中,在200℃下反应3小时。
(4)离心,清洗。
实施例7
用未包覆的铜纳米线和实施例3中碳包覆铜纳米线制备透明导电薄膜,导电薄膜的制备方法如下:先利用过滤法在硝酸纤维素滤膜沉积一层铜纳米线或碳包覆铜纳米线,然后将滤膜含有纳米线面朝向衬底压紧,最后用丙酮除去纤维素滤膜。薄膜导电性和透光性对比见表1。
表1 CuNWs和CuNWs@C透明导电薄膜透光性和导电性对比, T550为薄膜在光波长为550nm处的透过率。
实施例8
用未包覆的铜纳米线和实施例3中碳包覆铜纳米线制备透明导电薄膜。导电薄膜的制备方法如下:先利用过滤法在硝酸纤维素滤膜沉积一层铜纳米线或碳包覆铜纳米线,然后将滤膜含有纳米线面朝向衬底压紧,最后用丙酮除去纤维素滤膜。导电薄膜置于空气中(RH=20%, T=20℃)保存,观察其导电性的变化,结果如图3所示。可见经过500小时后未包覆的铜纳米线薄膜电阻增加了超过150倍,而碳包覆的铜纳米导电薄膜电阻则没有明显变化。
实施例9
以未包覆的铜纳米线和实施例3中碳包覆铜纳米线制备透明导电薄膜。导电薄膜的制备方法如下:先利用过滤法在硝酸纤维素滤膜沉积一层铜纳米线或碳包覆铜纳米线,然后将滤膜含有纳米线面朝向衬底压紧,最后用丙酮除去纤维素滤膜。导电薄膜作为导电基底,在其上旋涂聚苯胺薄膜(PANI)薄膜作为对电极应用于染料敏化太阳能电池(DSC)。所述的染料敏化太阳能电池光阳极为约10um厚的多孔TiO2薄膜,染料为N719,电解质的组分是:0.1M LiI, 0.05M I2, 0.6M PMII (1-甲基-3-丙基咪唑碘),0.5M TBP (四叔丁基吡啶),溶剂:碳酸丙烯酯和乙腈(1/1, vol/vol)。测试条件是AM1.5G 模拟光源,强度为100mW/cm2,电池有效面积是0.25cm2。
由于碘电解质强烈的腐蚀性,未包覆的铜纳米线薄膜很快便会被腐蚀,因而无法应用于DSC。而碳包覆的铜纳米线薄膜则可以很好地抵抗电解质的腐蚀,所得电池的效率甚至优于同等条件下使用FTO时所获得的效率(如图4)。
Claims (3)
1.一种碳包覆金属纳米线导电薄膜的制备方法,其特征在于,包含以下步骤:
(1)配制异丙醇和水的混合溶液,其中异丙醇和水的体积比为1-2,再往溶液中加入0.03-0.2g/ml量的葡萄糖;
(2)往(1)溶液中加入一定量的金属纳米线,金属纳米线和葡萄糖的摩尔比为0.01-0.1;
(3)将(2)溶液按50%的体积比填充度置于反应釜中,在160-200℃下反应1-5小时;
(4)离心,清洗,再分散;
(5)利用(4)制备的碳包覆金属纳米线通过喷涂或膜转移方法制备透明导电薄膜。
2.根据权利要求1所述的制备方法,其特征在于,所述的金属纳米线为金纳米线、银纳米线、铜纳米线中的一种或几种,或为金、银、铜合金的纳米线。
3.根据权利要求1所述的制备方法,其特征在于,铜纳米线的制备方法如下:
将50mg 二水氯化亚铜,300 十六胺,150mg 葡萄糖溶于20ml 的去离子水中,100摄氏度加热反应6小时生成铜纳米线,提纯后分散于异丙醇中得到铜纳米线分散液。
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