CN109473285A - 一种基于BiFeO3铁电效应的高性能光电化分解水光阳极及其制备方法 - Google Patents
一种基于BiFeO3铁电效应的高性能光电化分解水光阳极及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种基于BiFeO3铁电效应的高性能光电化分解水光阳极及其制备方法。本发明以FTO为衬底制备TiO2薄膜,BiFeO3薄膜复合于TiO2薄膜之上;通过施加正反向电压来对BiFeO3薄膜进行铁电极化,将TiO2的半导体性能和BiFeO3的铁电特性相结合。本发明实现了复合光阳极对可见光的响应能力,提高了光阳极的光电化学性能。通过对BiFeO3薄膜本身的铁电效应来改变其内建电场,从而有效的调控界面的能带结构,以期有效对载流子进行分离,从而提高光阳极的光电化学性能。结构简单,易于规模生产,具有良好的应用前景。
Description
技术领域
本发明属于清洁可再生新能源利用技术领域,涉及一种基于BiFeO3铁电效应的高性能光电化分解水光阳极及其制备方法。
背景技术
在当前能源与环境问题日益突出的大背景下,寻找清洁可持续的新能源替代传统化石能源正受到人们越来越多的关注。太阳能作为取之不尽同时又是生态学上纯净的和不改变地球上燃料平衡的能源,只要能以10%效率转化0.1%到达地球表面的太阳能,即可满足全球的能源需求。因此,太阳能是未来人类社会构建低碳经济时代最理想的能源,开发高效的太阳能利用方式也成为当前科学家的重大研究课题。光电化学分解水技术是在电场辅助下的光电化学分解水,光电催化氧化还原反应发生在不同的电极上,能够减少光生电子空穴对的复合几率,进而提升了能量转换效率,同时,光电化学分解水技术具有对环境零污染等特点,因而受到越来越广泛的研究和应用,是最具前景的太阳能转化利用方法之一,也被认为是解决能源短缺和环境污染问题最理想的途径之一。
为获得高效的光电化学分解水过程,实现光阳极材料吸收光谱波段的最大化和界面处载流子分离和传输能耗的最小化尤为关键。但实际的研究表明,开发一个在这两个要素上均有显著提高的光电化学光阳极十分困难。目前的光阳极材料主要分为两大类:窄带隙的半导体(硅,III-V族化合物等)和宽带隙的金属氧化物(TiO2,ZnO等)。窄带隙半导体因光腐蚀和光钝化导致其稳定性能较差。宽带隙的金属氧化物电极,尤其是TiO2,因其成本低廉且具有出色的光电化学稳定性及多样的形貌结构受到了广泛的研究。不过,由于TiO2材料本身带宽较大,对太阳能吸光波段较小,使得光电转化效率较低(当带宽大于3.0eV,光电转化效率小于2%)。
本专利提供了一种既能拓宽TiO2的吸光范围,又能提高载流子的分离传输效率的方法。铁酸铋(BiFeO3)属于多铁材料的一种,禁带宽度约为2.12eV,可以吸收可见光。同时,由于Bi离子具有孤对电子,因而,BiFeO3还有好的铁电极化性能,其自发极化值为100μC/cm2。本专利正是利用BiFeO3的可见光响应和铁电极化性能来拓宽TiO2的吸光范围,提高载流子的分离传输效率。
发明内容
本发明的目的就是提供一种基于BiFeO3铁电效应的高性能光电化分解水光阳极及其制备方法。
本发明包括FTO/TiO2/BiFeO3复合光阳极,由TiO2薄膜和BiFeO3薄膜组成,以FTO为衬底制备TiO2薄膜,BiFeO3薄膜复合于TiO2薄膜之上;TiO2薄膜的厚度为20~100nm,BiFeO3薄膜的厚度为20~100nm。通过施加正反向电压来对BiFeO3薄膜进行铁电极化,外加正反向极化电压范围为2~10V。通过将TiO2的半导体性能和BiFeO3的铁电特性相结合,利用BiFeO3增强复合光阳极对可见光的吸收,通过正反向电压极化来改变BiFeO3薄膜的内建电场,从而调控TiO2/BiFeO3界面的能带结构;在正向极化下,极化方向与自发极化方向一致,内建电场增强,TiO2/BiFeO3界面势垒高度会增加,抑制了光生载流子的复合,提高了载流子的分离传输性能;而在反向极化下,TiO2/BiFeO3界面势垒高度会减小,不利于光生载流子的分离。
所述的FTO直接购买得到。
所述的TiO2薄膜采用旋涂法制备,旋涂液由10ml无水乙醇,0.7ml钛酸异丙酯,0.5ml的盐酸组成;旋涂速度5000转/秒,在500℃下进行退火;TiO2薄膜的厚度为20~100nm,通过改变旋涂次数来改变薄膜的厚度。
所述的BiFeO3薄膜采用旋涂法制备,旋涂液由2mM硝酸铁,2.5mM硝酸铋,1.86克柠檬酸溶解在4ml的乙二醇中组成,旋涂速度5000转/秒,并在500℃下进行退火。BiFeO3薄膜的厚度为20~100nm,通过改变旋涂次数来改变薄膜厚度。
作为优选,所述的外加正反向极化电压范围为4~6V,正向极化时BiFeO3薄膜连接电源正极,反向极化时BiFeO3薄膜连接电源负极。
作为优选,所述的BiFeO3薄膜的厚度为30~60nm。
本发明成功实现了复合光阳极对可见光的响应能力,提高了光阳极的光电化学性能。同时,本发明通过对BiFeO3薄膜本身的铁电效应来改变其内建电场,从而有效的调控界面的能带结构,以期有效对载流子进行分离,从而提高光阳极的光电化学性能。本发明的光阳极结构简单,易于规模生产,具有良好的应用前景。
附图说明
图1为TiO2及BFO/TiO2的紫外可见吸收谱图;
图2为可见光下TiO2及BFO/TiO2的I-V曲线图;
图3为AM1.5G光照时TiO2及BFO/TiO2的I-V曲线图;
图4为可见光下不同极化条件下TiO2及TiO2/50nmBiFeO3的I-V曲线图;
图5为AM1.5G光照时,不同极化条件下TiO2及TiO2/50nmBiFeO3的I-V曲线图。
具体实施方式
实施例1:TiO2薄膜厚度30nm,BiFeO3薄膜厚度为30nm,封装后作为光阳极,饱和甘汞电极作为参比电极,Pt片为对电极,电解质溶液为1M的NaOH水溶液。由图1可见,相较于纯TiO2,TiO2/30nmBiFeO3复合光阳极在可见光区的吸光性能明显增强。由图2及图3可以看出,可见光及AM1.5G下的光电流密度明显增大。
实施例2:TiO2薄膜厚度30nm,BiFeO3薄膜厚度为50nm,封装后作为光阳极,饱和甘汞电极作为参比电极,Pt片为对电极,电解质溶液为1M的NaOH水溶液。铁电极化效应通过外加5V的正反向电压来实现。正向极化时BiFeO3薄膜连接电源正极,FTO接电源负极,反向极化时BiFeO3薄膜连接电源负极,FTO接电源正极。由图1可见,相较于纯TiO2,TiO2/50nmBiFeO3复合光阳极在可见光区的吸光性能明显增强。同时,由图2及图3可以看出,可见光及AM1.5G下的光电流密度明显增大。相较于纯TiO2,在可见光下,1.5V时的电流密度由0.739mA/cm2提高到15.17mA/cm2,提高了近20倍。在AM1.5G下,1.5V时的电流密度由1.497mA/cm2提高到17.39mA/cm2,提高了近12倍。更重要的是,对TiO2/50nmBiFeO3复合光阳极在外加电压下进行极化,由图4及图5可以看出,在正向5v的极化电压下,不论在可见光还是AM1.5G下,TiO2/50nmBiFeO3的光电流密度较未极化时有了进一步的明显增加。在可见光下,正向极化后,1.5V时的电流密度由15.17mA/cm2提高到23.03mA/cm2,提高了52%。在AM1.5G下,1.5V时的电流密度由17.39mA/cm2提高到28.67mA/cm2,提高了64.8%。而在反向5v的极化电压下,不论在可见光还是AM1.5G下,TiO2/50nmBiFeO3的光电流密度较未极化时有了明显的降低。
实施例3:TiO2薄膜厚度30nm,BiFeO3薄膜厚度为80nm,封装后作为光阳极,饱和甘汞电极作为参比电极,Pt片为对电极,电解质溶液为1M的NaOH水溶液。由图1可见,相较于纯TiO2,TiO2/80nmBiFeO3复合光阳极在可见光区的吸光性能明显增强。同时,由图2及图3可以看出,可见光及AM1.5G下的光电流密度有所增大。
上述实施例并非是对于本发明的限制,本发明并非仅限于上述实施例,只要符合本发明要求,均属于本发明的保护范围。
Claims (4)
1.一种基于BiFeO3铁电效应的高性能光电化分解水光阳极,其特征在于:包括FTO/TiO2/BiFeO3复合光阳极,由TiO2薄膜和BiFeO3薄膜组成,以FTO为衬底制备TiO2薄膜,BiFeO3薄膜复合于TiO2薄膜之上;TiO2薄膜的厚度为20~100nm,BiFeO3薄膜的厚度为20~100nm;通过施加正反向电压来对BiFeO3薄膜进行铁电极化,外加正反向极化电压范围为2~10V;通过将TiO2的半导体性能和BiFeO3的铁电特性相结合,利用BiFeO3增强复合光阳极对可见光的吸收,通过正反向电压极化来改变BiFeO3薄膜的内建电场,从而调控TiO2/BiFeO3界面的能带结构。
2.如权利要求1所述的一种基于BiFeO3铁电效应的高性能光电化分解水光阳极的其制备方法,其特征在于:所述的TiO2薄膜采用旋涂法制备,旋涂液由10ml无水乙醇,0.7ml钛酸异丙酯,0.5ml的盐酸组成;旋涂速度5000转/秒,在500℃下进行退火;TiO2薄膜的厚度为20~100nm,通过改变旋涂次数来改变薄膜的厚度;
所述的BiFeO3薄膜采用旋涂法制备,旋涂液由2mM硝酸铁,2.5mM硝酸铋,1.86克柠檬酸溶解在4ml的乙二醇中组成,旋涂速度5000转/秒,并在500℃下进行退火;BiFeO3薄膜的厚度为20~100nm,通过改变旋涂次数来改变薄膜厚度。
3.如权利要求1所述的一种基于BiFeO3铁电效应的高性能光电化分解水光阳极,其特征在于:所述的外加正反向极化电压范围为4~6V,正向极化时BiFeO3薄膜连接电源正极,反向极化时BiFeO3薄膜连接电源负极。
4.如权利要求1或2所述的一种基于BiFeO3铁电效应的高性能光电化分解水光阳极,其特征在于:所述的BiFeO3薄膜的厚度为30~60nm。
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