CN109054837B - 一种稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的制备方法 - Google Patents
一种稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的制备方法 Download PDFInfo
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Abstract
一种稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的制备方法,本发明涉及NaYF4:Yb3+/Er3+@BiOCl复合材料的制备方法。本发明是要解决现有的NaYF4:Yb3+/Er3+上转换基染料敏化太阳能电池的光电转换效率低的技术问题。本方法:一、配制BiCl3溶液;二、将NaYF4:Yb3+/Er3+加入到BiCl3溶液中反应,得到BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶;三、将BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶烧结,得到稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶。用该纳米晶制备的染料敏化太阳能电池的光阳极,电池效率比未处理的NaYF4:Yb3+/Er3+提高10%~14%,可用于染料敏化太阳能电池中。
Description
技术领域
本发明涉及NaYF4:Yb3+/Er3+@BiOCl复合材料的制备方法。
背景技术
目前有效利用的太阳光仅占到达地球表面太阳能的万分之一,人们期望太阳能将来能够满足大部分能量需求。染料敏化太阳能电池(DSSCs)因其价格低廉、无污染和相对较高的光电转换效率被认为是硅基太阳能电池的理想替代者,N719作为其核心染料,仅能吸收400-700nm可见波段太阳光光子而无法利用占太阳光谱中约55%的红外太阳光光子,致使电池光电转换效率的提升受到限制。上转换过程能将两个低于N719带隙能量的光子进行叠加,并发射出一个大于N719带隙能量的上转换光子,在染敏太阳能电池中应用上转换材料能有效提高电池效率。NaYF4:Yb3+/Er3+上转换纳米晶是目前发光效率最高的上转换材料,并已被广泛用于增强染料敏化太阳能电池对红外光的响应,尽管上转换基染料敏化太阳能电池的光电转换效率得到了一定提升,但是增加的幅度非常有限,这是因为 NaYF4纳米晶是绝缘物质所造成的,当其掺杂到光阳极中会严重阻碍光电子在光阳极中传输,从而使电池效率提高受阻。
发明内容
本发明是要解决现有的NaYF4:Yb3+/Er3+上转换基染料敏化太阳能电池的光电转换效率低的技术问题,而提供一种稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的制备方法。
本发明的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的制备方法,按以下步骤进行:
一、将BiCl3加入到乙二醇中,加热至60~65℃并搅均匀,得到BiCl3溶液;
二、将NaYF4:Yb3+/Er3+加入到BiCl3溶液中,搅拌均匀,冷却至室温,并调节溶液的pH=8~9,重新加热至60~65℃并搅拌反应0.5~1h后,冷却静置,除去上层清液,加入乙醇搅拌均匀后,放在烘箱中,在40~60℃的条件下进行干燥处理,得到BiOCl包覆的 NaYF4:Yb3 +/Er3+纳米晶;
三、将步骤二制备的BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶放在氧化铝坩埚中,再将氧化铝坩埚放在马弗炉中,在空气气氛中升温至200~300℃烧结1~3h,自然降温,得到稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶。
本发明的方法是将六棱柱NaYF4:Yb3+/Er3+内核直接掺入到BiCl3乙二醇溶液中,以NaYF4:Yb3+/Er3+内核作为晶种,在其外表面外延生长一层BiOCl的壳层结构,再将BiOCl 包覆的NaYF4:Yb3+/Er3+纳米晶粉末进行烧结处理,从而获得结构稳定的 NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶。NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶是一种灰白色粉末,六方相NaYF4:Yb3+/Er3+@BiOCl纳米晶体尺寸约为0.6~1.5μm。通过烧结处理,可促进壳层BiOCl牢固包覆在NaYF4:Yb3+/Er3+表面,将其应用于染料敏化太阳能电池的光阳极,电池效率比未处理前的NaYF4:Yb3+/Er3+提高10%~14%,这是因为NaYF4本身不具有导电性质,对光阳极中电子的传输无促进作用,而BiOCl是一种半导体材料,可促进光电子传输并提高上转换效率,从而有效提升染料敏化太阳能电池的光电转换效率。
本发明所用设备简单,原料成本低廉,操作过程方便,反应过程所需原料低毒,无害,
本发明制备的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶可用于染料敏化太阳能电池中。
附图说明
图1是实施例1中步骤二中原材料NaYF4:Yb3+/Er3+的扫描电镜照片;
图2是实施例1中步骤二中得到的BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶的扫描电镜照片;
图3是实施例1中步骤三中得到的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的扫描电镜照片;
图4是实施例1中NaYF4:Yb3+/Er3+、步骤二得到的BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶、步骤三得到的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的XRD谱图;
图5是实施例1中,NaYF4:Yb3+/Er3+纳米晶、BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶、稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶修饰的染料敏化太阳能电池的伏安特性曲线;
图6是实施例2中步骤三中得到的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的扫描电镜照片;
图7是实施例2中步骤三中得到的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的扫描电镜照片。
具体实施方式
具体实施方式一:本实施方式的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的制备方法,按以下步骤进行:
一、将BiCl3加入到乙二醇中,加热至60~65℃并搅均匀,得到BiCl3溶液;
二、将NaYF4:Yb3+/Er3+加入到BiCl3溶液中,搅拌均匀,冷却至室温,并调节溶液的pH=8~9,重新加热至60~65℃并搅拌反应0.5~1h后,冷却静置,除去上层清液,加入乙醇搅拌均匀后,放在烘箱中,在40~60℃的条件下进行干燥处理,得到BiOCl包覆的 NaYF4:Yb3 +/Er3+纳米晶;
三、将步骤二制备的BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶放在氧化铝坩埚中,再将氧化铝坩埚放在马弗炉中,在空气气氛中升温至200~300℃烧结1~3h,自然降温,得到稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶。
具体实施方式二:本实施方式与具体实施方式一不同的是步骤一中BiCl3的物质的量与乙二醇的体积的比为1mmol:(15~20)mL。其它与具体实施方式一相同。
具体实施方式三:本实施方式与具体实施方式一或二不同的是步骤二中 NaYF4:Yb3+/Er3+与BiCl3的摩尔比为1:(0.1~0.2)。其它与具体实施方式一或二相同。
具体实施方式四:本实施方式与具体实施方式一至三之一不同的是步骤一中所述的 NaYF4:Yb3+/Er3+中,Yb3+的掺杂摩尔百分数为10%~20%,Er3+的掺杂摩尔百分数为0.5%~2%。其它与具体实施方式一至三之一相同。
具体实施方式五:本实施方式与具体实施方式一至四之一不同的是:步骤一中所述的 NaYF4:Yb3+/Er3+是通过下面的方法制备的:
一、按Y(NO3)3、Yb(NO3)3和Er(NO3)3的总摩尔浓度为2~2.5mol/L、Yb3+的摩尔百分数为10%~20%、Er3+的摩尔百分数为0.5%~2%、Y3+的摩尔百分数为78%~89.5%,将 Y(NO3)3、Yb(NO3)3和Er(NO3)3加入去离子水中,溶解,得到稀土溶液;
二、向稀土溶液中加入柠檬酸钠水溶液;其中柠檬酸钠与稀土的摩尔比为1:(1~1.2);搅拌均匀后,再加入氟化钠水溶液;其中氟化钠与稀土的摩尔比为(1.1~1.2):1;再搅拌均匀后,得到混合液;
三、将混合液移入至反应釜中,在180~190℃的条件下水热反应24~28小时,清洗、干燥后,得到NaYF4:Yb3+/Er3+纳米晶。
其它与具体实施方式一至四之一相同。
具体实施方式六:本实施方式与具体实施方式一至五之一不同的是步骤三中升温速率为5~15℃/min。其它与具体实施方式一至五之一相同。
用下面的实施例验证本发明的有益效果:
实施例1:本实施例的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的制备方法,按以下步骤进行:
一、将0.0315g BiCl3加入到15ml乙二醇中,加热至60℃并搅搅拌5分钟,得到均匀的BiCl3溶液;
二、将0.1845gNaYF4:Yb3+/Er3+加入到步骤一得到的BiCl3溶液中,搅拌均匀,冷却至室温,并调节溶液的pH=8,重新加热至60℃并搅拌反应1h后,冷却静置,除去上层清液,加入10ml乙醇搅拌均匀后,放在烘箱中,在60℃的条件下进行干燥8小时,得到 BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶;
三、将步骤二制备的BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶放在氧化铝坩埚中,再将氧化铝坩埚放在马弗炉中,在空气气氛中以10℃/min的升温速率升温至200℃烧结2h,自然降温,得到稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶。
其中步骤二中所述的NaYF4:Yb3+/Er3+是通过下面的方法制备的:
在一个50mL烧杯中加入4mL浓度为4mol/L的柠檬酸钠水溶液和6mL Ln(NO3)3溶液,其中Ln(NO3)3溶液是按Y(NO3)3、Yb(NO3)3和Er(NO3)3的总摩尔浓度为 0.2mol/L、Yb3+的摩尔百分数为20%、Er3+的摩尔百分数为2%、Y3+的摩尔百分数为80%,将Y(NO3)3、Yb(NO3)3和Er(NO3)3加入去离子水中配制而成的;搅拌20分钟,随后加入28.8mL浓度为0.5mol/L的氟化钠水溶液,再搅拌30分钟后,将混合液移入50mL 反应釜中,在180℃下水热反应24小时,清洗、干燥后,得到NaYF4:Yb3+/Er3+纳米晶。
本实施例在步骤二中所用的原料NaYF4:Yb3+/Er3+的扫描电镜照片如图1所示,步骤二中得到的BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶的扫描电镜照片如图2所示,步骤三中得到的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的扫描电镜照片如图3所示,从图 1可以看出,NaYF4:Yb3+/Er3+纳米晶核外表面很干净,无杂质,从图2可以看出,BiOCl 包覆的NaYF4:Yb3+/Er3+纳米晶,其表面很粗糙,且明显看出表面有附着的松散的BiOCl 颗粒,结合不稳固;由图3可以看出,经过进一步热处理得到的NaYF4:Yb3+/Er3+@BiOCl 核壳结构纳米晶表面很均匀的包覆了一层BiOCl,未包覆上的BiOCl明显减少,且结构更加稳固。
本实施例步骤二的原料NaYF4:Yb3+/Er3+、步骤三得到的稳固的 NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的XRD谱图如图4所示,对比 NaYF4:Yb3+/Er3+@BiOCl和NaYF4以及BiOCl的两个标准XRD图可知,掺杂Yb3+/Er3+的NaYF4表面的确包覆了BiOCl,由于Yb3+/Er3+的掺杂量比较少,对NaYF4的晶相不会产生影响,因而看不到Yb3+和Er3+的衍射峰。
为证实稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶更有利于提升染料敏化太阳能电池性能,用原料NaYF4:Yb3+/Er3+、步骤二得到的BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶、步骤三得到的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶同时制备染料敏化太阳能电池,其中所述的染料敏化太阳能电池是通过下面的方法制备的:
a、制备浆料:称取0.25g乙基纤维素超声溶于10mL乙醇中,加入0.50g P25型TiO2粉体、2.17mL松油醇和0.0315g NaYF4:Yb3+/Er3+,搅拌1h,加热80℃除去多余乙醇,得到NaYF4:Yb3+/Er3+的浆料;再将NaYF4:Yb3+/Er3+替换为BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶,采用相同步骤得到BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶浆料;再将NaYF4:Yb3+/Er3+替换为稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶,得到稳固的 NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶浆料;得到三种浆料;
b、制备光阳极:吸取一滴浆料置于丝网印刷网面上,用刮刀进行刮涂,晾干后刮涂新的一层,共涂覆6层,马弗炉程序升温进行烧结,升温程序如表1所示,得到三种光阳极;
表1程序升温烧结步骤
c、将烧结完成的光阳极在70℃的浓度为30mmol/L的极稀的TiCl4水溶液中浸渍1h,取出并用去离子水冲洗3次,再在500℃条件下烧结30min。
d、染料的制备与浸渍:称取0.0119g N719溶于10mL无水乙醇中,超声分散,配成0.5mmol/L的溶液,将经步骤c烧好的光阳极降温至80℃,浸没于染料中放置24h。
e、制备对电极:称取0.052g H2PtCl6溶于10mL异丙醇中,超声分散,在FTO玻璃导电面合适位置上滴加一滴H2PtCl6溶液,空气中晾置10min,450℃下烧结0.5h,得到对电极。
f、电池的封装:将经步骤d处理后的光阳极置于回字形热封膜中央,然后将制作好的对电极放置在热封膜上方,并确保小孔在回字形内部,105℃按压热封。通过小孔向光阳极和对电极之间注入I3 –/I–电解质溶液,然后用热熔胶对小孔进行密封,得到三种染料敏化太阳能电池。
对三种电池进行J-V曲线测试,结果如图5所示,其数据如表2所示。
表2三种电池的性能
从图5和表1可以看出,以原料NaYF4:Yb3+/Er3+制备的电池,其电池效率达到6.232%,电流密度为12.425mA/cm2。而利用步骤二的BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶制备的电池,电池效率提升到6.658%,电流密度却降到11.766mA/cm2,电流密度的降低是由BiOCl与NaYF4:Yb3+/Er3+层间结构不稳定,致使加入光阳极后两种材料结构分离,会对光电子有淬灭作用所致。但是由于其依然具有较好的散射和吸收红外光源能量的作用使得电池效率得到有效的提高;当进一步采用步骤三得到的稳固的NaYF4:Yb3+/Er3+@BiOCl 核壳结构纳米晶制备的电池,电池的光电转换效率提升到6.886%,短路电流密度提升到 12.836mA/cm2,较NaYF4:Yb3+/Er3+提高了电池基础效率的10.49%,该结果表明步骤三制备的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶兼具吸收近红外光同时有助于光阳极电子传输,从而有效的提高了染料敏化太阳能电池的光电转换效率。
实施例2:本实施例的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的制备方法,按以下步骤进行:
一、将0.0315g BiCl3加入到15ml乙二醇中,加热至60℃并搅搅拌5分钟,得到均匀的BiCl3溶液;
二、将0.1845gNaYF4:Yb3+/Er3+加入到步骤一得到的BiCl3溶液中,搅拌均匀,冷却至室温,并调节溶液的pH=8.5,重新加热至60℃并搅拌反应1h后,冷却静置,除去上层清液,加入10ml乙醇搅拌均匀后,放在烘箱中,在60℃的条件下进行干燥8小时,得到BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶;其中NaYF4:Yb3+/Er3+的制备方法与实施例1 相同;
三、将步骤二制备的BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶放在氧化铝坩埚中,再将氧化铝坩埚放在马弗炉中,在空气气氛中以15℃/min的升温速率升温至280℃烧结2h,自然降温,得到稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶。
本实施例制备的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的扫描电镜照片如图6所示,由图6可以看出,本实施例得到的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的表面均匀牢固地包覆了一层BiOCl。
利用本实施例制备的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶制备染料敏化太阳能电池进行测试,其电流密度为12.647mA/cm2,开路电压为0.745V,电池效率为6.860%。
实施例3:本实施例的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的制备方法,按以下步骤进行:
一、将0.0315g BiCl3加入到15ml乙二醇中,加热至60℃并搅搅拌5分钟,得到均匀的BiCl3溶液;
二、将0.1845gNaYF4:Yb3+/Er3+加入到步骤一得到的BiCl3溶液中,搅拌均匀,冷却至室温,并调节溶液的pH=9,重新加热至60℃并搅拌反应1h后,冷却静置,除去上层清液,加入10ml乙醇搅拌均匀后,放在烘箱中,在60℃的条件下进行干燥8小时,得到 BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶;其中NaYF4:Yb3+/Er3+的制备方法与实施例1相同;
三、将步骤二制备的BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶放在氧化铝坩埚中,再将氧化铝坩埚放在马弗炉中,在空气气氛中以15℃/min的升温速率升温至300℃烧结3h,自然降温,得到稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶。
本实施例制备的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的扫描电镜照片如图7所示,由图7可以看出,本实施例得到的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的表面均匀牢固地包覆了一层BiOCl。
利用本实施例制备的稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶制备染料敏化太阳能电池进行测试,其电流密度为12.772mA/cm2,开路电压为0.745V,电池效率为6.872%。
Claims (6)
1.一种稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的制备方法,其特征在于该方法按以下步骤进行:
一、将BiCl3加入到乙二醇中,加热至60~65℃并搅均匀,得到BiCl3溶液;
二、将NaYF4:Yb3+/Er3+加入到BiCl3溶液中,搅拌均匀,冷却至室温,并调节溶液的pH=8~9,重新加热至60~65℃并搅拌反应0.5~1h后,冷却静置,除去上层清液,加入乙醇搅拌均匀后,放在烘箱中,在40~60℃的条件下进行干燥处理,得到BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶;
三、将步骤二制备的BiOCl包覆的NaYF4:Yb3+/Er3+纳米晶放在氧化铝坩埚中,再将氧化铝坩埚放在马弗炉中,在空气气氛中升温至200~300℃烧结1~3h,自然降温,得到稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶。
2.根据权利要求1所述的一种稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的制备方法,其特征在于步骤一中BiCl3的物质的量与乙二醇的体积的比为1mmol:(15~20)mL。
3.根据权利要求1或2所述的一种稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的制备方法,其特征在于步骤二中NaYF4:Yb3+/Er3+与BiCl3的摩尔比为1:(0.1~0.2)。
4.根据权利要求1或2所述的一种稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的制备方法,其特征在于步骤二中所述的NaYF4:Yb3+/Er3+中,Yb3+的掺杂摩尔百分数为10%~20%,Er3+的掺杂摩尔百分数为0.5%~2%。
5.根据权利要求1或2所述的一种稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的制备方法,其特征在于步骤二中所述的NaYF4:Yb3+/Er3+是按以下步骤制备的:
一、按Y(NO3)3、Yb(NO3)3和Er(NO3)3的总摩尔浓度为2~2.5mol/L、Yb3+的摩尔百分数为10%~20%、Er3+的摩尔百分数为0.5%~2%、Y3+的摩尔百分数为78%~89.5%,将Y(NO3)3、Yb(NO3)3和Er(NO3)3加入去离子水中,溶解,得到稀土溶液;
二、向稀土溶液中加入柠檬酸钠水溶液;其中柠檬酸钠与稀土的摩尔比为1:(1~1.2);搅拌均匀后,再加入氟化钠水溶液;其中氟化钠与稀土的摩尔比为(1.1~1.2):1;再搅拌均匀后,得到混合液;
三、将混合液移入至反应釜中,在180~190℃的条件下水热反应24~28小时,清洗、干燥后,得到NaYF4:Yb3+/Er3+纳米晶。
6.根据权利要求1或2所述的一种稳固的NaYF4:Yb3+/Er3+@BiOCl核壳结构纳米晶的制备方法,其特征在于步骤三中升温速率为5~15℃/min。
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Inventor after: Hao Shuwei Inventor after: Jiao Dandan Inventor after: Hou Yuedan Inventor after: Yang Chunhui Inventor after: Na Hongzhuang Inventor before: Hao Shuwei Inventor before: Hou Yuedan Inventor before: Yang Chunhui |