CN107818871A - 一种染料敏化太阳能电池对电极的制备方法 - Google Patents
一种染料敏化太阳能电池对电极的制备方法 Download PDFInfo
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- H—ELECTRICITY
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- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
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- H—ELECTRICITY
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- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2054—Light-sensitive devices comprising a semiconductor electrode comprising AII-BVI compounds, e.g. CdTe, CdSe, ZnTe, ZnSe, with or without impurities, e.g. doping materials
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Abstract
本发明涉及一种染料敏化太阳能电池对电极的制备方法,首先将碳布分别置于丙酮和乙醇中超声清洗,碳布的沉积面积控制在1×3cm2;配制三元铜锌锡镀液;在铜锌锡镀液中,采用恒电势电沉积技术制得得到CZT/碳布预制电极;将预制电极进行溶剂热反应制得本发明的对电极。本发明采用电沉积后溶剂热处理在碳布上原位生长结晶性优异且不含杂相的CZTSe米结构,所制备的对电极较传统Pt对电极具有更优的电催化活性及更快的电子传输速率,利用其组装的太阳能电池的光电效率优于基于Pt对电极组装的电池光电效率,该制备技术简单高效,可实现柔性敏化太阳能电池的大面积制备与推广。
Description
技术领域
本发明涉及一种染料敏化太阳能电池对电极的制备方法,属于太阳能电池技术领域。
背景技术
从Cu2ZnSnSe4(CZTSe)作为对电极材料应用在染料敏化太阳能电池(DSSCs)中获得了3.62%的光电转换效率起,CZTSe就已被证实是一种环保、高效及对电解质中的I3 -具有优异的催化还原性能的催化材料,逐渐成为敏化电池体系中替代Pt对电极材料的研究热点。近年来,各国科研人员相继开发了几种制备CZTSe薄膜对电极的方法,包括基于真空条件的沉积策略(脉冲激光沉积法、蒸发和磁控溅射法)、静电纺丝法和基于溶液处理的工艺(溶剂热法/热解法/溶胶凝胶法获得CZTSe前驱颗粒后真空/硫化退火)。上述提及的方法中,溶液处理的方法具有成本低廉和工艺简单的特点,更适用于制备大面积、高效的DSSCs用对电极。此外,通过控制改变反应中使用的溶剂、长链表面活性剂和反应物类型,可以轻易获得具有大比表面积的纳米结构,以此来改善对电极材料的催化还原性能。然而,基于溶液处理的CZTSe薄膜对电极的制备流程包括两步,首先,采用旋涂、刮涂或喷涂的方法将CZTSe墨水/前驱体涂覆在基底上,获得纳米结构的CZTSe预制薄膜;随后,需要选择繁琐严苛的真空退火或硫化退火的工艺处理预制薄膜,以此来获得无杂相、结晶性优异且催化活性强的CZTSe薄膜对电极,需要指出的是,处理的环境为高真空条件,退火温度区间通常在300-600℃,选用有毒的硫化氢或硫蒸气为处理气氛。这对于基于导电塑料为基底的对电极的制备来说,上述工艺将不再适用,这主要是因为导电塑料不能经受超过150℃的热处理。到目前为止,还未见报导不使用真空退火或硫化退火工艺制备CZTSe对电极材料的策略,因此,基于获得结晶性优异、化学稳定性好及高效的CZTSe对电极的前提下,开发出一种简易、廉价、环保且温和的原位制备方法尤为重要。
发明内容
本发明所要解决的技术问题在于克服上述缺陷,提供一种染料敏化太阳能电池对电极的制备方法。
基于上述目的,本发明采取了如下技术方案:
一种染料敏化太阳能电池对电极的制备方法,包括以下步骤:
(1)将碳布分别置于丙酮和乙醇中超声清洗,碳布的沉积面积控制在1×3cm2;
(2)配制三元铜锌锡镀液;
(3)采用电化学工作站组成的三电极体系,以步骤(1)中清洗好的碳布为工作电极、铂片(3×3cm2)为对电极、饱和甘汞电极为参比电极,保证工作电极与对电极正面相对,同时浸泡插入步骤(2)中的铜锌锡镀液中,进行恒电势电沉积,沉积结束后用蒸馏水和乙醇交替清洗碳布,置于烘箱中干燥,得到CZT/碳布预制电极;
(4)称取0.5-5mM硒粉置于聚四氟乙烯模具的聚四氟乙烯内衬中,放入步骤(3)制得的CZT/碳布预制电极,并固定于聚四氟乙烯模具中,将无水乙醇转移至内衬中,使液体体积达到内衬体积的70%,随后直接将内衬密封于不锈钢反应釜中,200℃下溶剂热反应1-48h,冷却至室温后,得到黑色的产物即为染料敏化太阳能电池对电极(CZTSe@碳布复合对电极)。
步骤(2)中,配制三元铜锌锡镀液的方法:首先称取50mM二水柠檬酸钠,加入去离子水搅拌使其溶解均匀,得到澄清透明溶液,随后依次加入3.5mM五水硫酸铜、20mM一水硫酸锌和2.1mM硫酸亚锡,充分搅拌使其溶解均匀,获得含三种金属离子的澄清蓝色镀液。
步骤(3)中,恒电势电沉积的的工作参数如下:电势范围为-1.0V至-1.5V,沉积时间为30s至1200s,电沉积环境温度为22℃。
步骤(4)中,硒粉的用量为2mM。
本发明的CZTSe@碳布复合对电极可以直接用于给太阳能电池组装,组装方法:将经N719染料敏化的柔性透明的TiO2/ITO/PEN光阳极和CZTSe@碳布复合对电极夹在一起,其中PEN上预留小孔,由小孔注入含碘电解质,光阳极和对电极之间通过沙林膜热压粘合封装成三明治结构,即得染料敏化太阳能电池。
本发明的有益效果在于:(1)本发明通过电沉积后溶剂热技术,可在柔性碳布上原位生长结晶性优异且不含杂相的CZTS纳米结构,相比于其它制备方法来说,制备工艺简单、高效便捷、无需后续退火过程;(2)本发明的对电极制备周期短,其制备过程环保无污染;(3)本发明制备过程所使用的化学试剂为常用试剂、绿色环保、廉价易得、易于大规模应用及推广;(4)本发明所获得的对电极表现出了高稳定性和柔性的优势,这种织物型复合催化对电极材料适用于制备高效、可穿戴、复杂曲面基板和低廉的DSSCs;(5)本发明的对电极具有比传统Pt电极更优异的电催化性能和电荷传输速率,作为对电极用于柔性染料敏化太阳能电池表现出比基于Pt对电极更好的光电转换效率,在一个模拟标准太阳光照射下(AM1.5,100mW/cm2),基于CZTSe@碳布复合对电极组装的柔性DSSCs的光电转换效率高达7.53%,短路电流密度、开路电压和填充因子分别为15.26mA/cm2、0.76V和64.57%。
附图说明
图1为实施例1所制备对电极的扫描电镜图;
图2为实施例1所制备对电极的激光拉曼图谱;
图3为实施例1所制备对电极的透射电镜照片;
图4为利用实施例1所制备对电极组装的染料敏化太阳能电池的电流密度-电压曲线;
图5为利用实施例1制备的对电极组装的太阳能电池的电化学阻抗图谱。
具体实施方式
下面结合附图和具体实施例对本发明的技术方案作进一步详细说明,但本发明的保护范围并不局限于此。
实验药品及试剂材料
五水硫酸铜、一水硫酸锌、硫酸亚锡、柠檬酸钠.二水(分析纯,国药集团化学试剂有限公司),无水乙醇、乙二醇、N,N-二甲基乙酰胺(分析纯,南京化学试剂有限公司),硒粉(分析纯,阿拉丁试剂有限公司),TiO2浆料(昆山桑莱特新能源科技有限公司),N719染料(澳大利亚Dyesol公司),Surlynl702热封薄膜、DHS-Et23液体碘电解质(大连七色光太阳能科技开发有限公司)。
实验设备仪器
选用CHI660E型电化学工作站(上海辰华仪器有限公司)进行电沉积,选用德国BRUKER Advance D8的X射线衍射仪(XRD)对样品进行物相结构表征分析,选用日本SU-4800的场发射扫描电子显微镜(SEM)对样品进行微观形貌观察,选用法国Horiba Jobin YvonHR800的激光拉曼对样品进行物相结构表征分析,选用荷兰FEI公司Tecnai G2型透射电镜(TEM)观察样品的微观形貌及结构特征,选用美国Newport,91192太阳光模拟器对对电极组装的染料敏化电池进行电流密度-电压曲线的测试。
实施例1
染料敏化太阳能电池对电极(CZTSe@碳布复合对电极)的制备:
第一步,碳布置于无水乙醇和丙酮中分别超声清洗并吹干待用,无需酸化亲水前处理,碳布的沉积面积控制在1×3cm2;
第二步,配置三元铜锌锡镀液,首先在烧杯中称取50mM柠檬酸钠.二水,加入去离子水搅拌使其溶解均匀,得到澄清透明溶液,随后分开依次加入3.5mM五水硫酸铜、20mM.一水硫酸锌和2.1mM硫酸亚锡,充分搅拌使其溶解均匀,获得含三种金属离子的澄清蓝色镀液;
第三步,电化学一步法在碳布上沉积铜锌锡前驱体,采用电化学工作站组成的三电极体系,以步骤二中清洗好的碳布为工作电极、铂片(3×3cm2)为对电极和饱和甘汞电极为参比电极,保证工作电极与对电极正面相对,同时浸泡插入步骤二中的铜锌锡镀液中,采用线性扫描曲线功能,电沉积电势为-1.17V,沉积时间为600s,电沉积环境温度控制在22℃,无需搅拌。沉积结束后用蒸馏水和乙醇交替清洗碳布,置于烘箱中干燥得到CZT/碳布预制电极;
第四步,称取2mM硒粉置于聚四氟乙烯内衬中,放入经去离子水清洗并吹干的CZT/碳布预制电极,并固定于聚四氟乙烯模具中,通过移液管将无水乙醇转移至内衬中,使液体体积达到内衬体积的70%,随后直接将内衬密封于不锈钢反应釜中,置于200℃烘箱中溶剂热反应24h,冷却至室温后,取出样品,即为黑色的CZTSe@碳布复合对电极,用乙醇冲洗并置于100℃烘干备用。
图1为本实施例制得的对电极的扫描电镜图,图1(a,b)是电沉积后的碳布,从图中可以看出,每根碳纤维都被均匀且致密的CZT颗粒覆盖,颗粒直径在70nm-100nm;图1(c,d)为CZTSe纳米片阵列在碳布上的扫描电镜照片,可以看出,CZTSe纳米片均匀有序地钉扎在每根碳纤维表面,纳米片的宽度和厚度分别为~390nm和~15nm。
图2为本实施例制得的对电极的激光拉曼图谱,从图中可以看出所得到的样品仅有CZTSe相存在(对应的拉曼峰位移为334cm-1),无其它硫化物杂相。由上述的结果可知,经过溶剂热处理24h可在碳布基底上生长纯净的CZTSe结构。
图3为本实施例制得的对电极的透射电镜照片,从图3(a)中可以看出,CZTSe呈不等边的片状结构,比表面积大,长边和短边的长度分别为340nm和245nm;图3(b)为纳米片边缘局部区域的高分辨透射电镜照片,可以看到取向排列一致的晶面,0.19nm和0.31nm的晶面间距分别对应Kesterite结构的CZTSe的(220)和(112)晶面;从图3(c)的CZTSe的SAED可知,清晰的衍射斑点出现在四方相的CZTSe中,证明了获得CZTSe纳米片为单晶结构且结晶性优异,其中的两组衍射斑点分别对应(112)和(220)晶面;图3(d)是单个纳米片上四种元素的面扫描能谱,所有元素都均匀地分布在纳米片上,无偏析。
将实施例1制得的对电极用于太阳能电池的组装:
(1)光阳极的制备:将经丙酮和乙醇交替清洗干净的ITO/PEN柔性导电基底置于50mM的TiCl4冰水溶液中70℃预处理1h,随后采用刮刀法在导电基底上涂覆TiO2浆料,再置于烘箱中于空气气氛下200℃退火5h,电池的面积通过3M魔术胶带控制在0.20cm2,厚度约为18μm。随炉冷却后的TiO2多孔层继续用TiCl4冰水溶液在70℃中预处理1h,以获得更多的染料吸附。随后在烘箱中80℃保温处理30min,取出后迅速将TiO2多孔层浸泡在含0.5mM的N719染料的乙醇溶液中,暗室静置24h以充分吸附染料,经无水乙醇冲去多孔层表面多余的染料后烘干得到TiO2光阳极;
(2)柔性DSSCs组装:DSSCs主要由TiO2光阳极和对电极中间灌装的液态电解质组成,将经N719染料敏化的柔性透明的TiO2/ITO/PEN光阳极和CZTSe@碳布复合对电极夹在一起,其中PEN上预留小孔,由小孔注入含碘电解质,光阳极和对电极之间通过沙林膜120℃热压粘合封装成三明治结构,即得太阳能电池。
图4为利用本实施例制得的对电极和空白碳布对电极组装的染料敏化太阳能电池的电流密度-电压曲线,从曲线上可以看出,制得的CZTSe@碳布复合对电极对电极组装的电池性能较空白的碳布有显著的提高,其光电转换效率高达7.53%,而空白碳布的效率仅为2.91%。大幅度增加的电流密度(15.26mA/cm2)是取得优异性能的原因,这表明空穴的再生速率在CZTS/碳布与电解质的界面比在单纯碳布与电解质的界面要快。此外,相比于空白碳布来说,CZTSe@碳布的填充因子从42.57增大至64.57%,填充因子主要影响电池器件整体的内部电阻,包括对电极材料的体电阻、接触电阻、光阳极内部的传输电阻和对电极与电解质界面间的传输电阻等。因此,CZTSe@碳布获得较大的电流密度和填充因子的原因是因为催化材料与电解质界面间电荷传输速率和整体催化能力的提高,进而降低了器件的整体电阻和电子与空穴的复合率。
图5为利用实施例1制得的对电极组装的太阳能电池的电化学阻抗图谱,通过Z-View软件拟合可得串联电阻(RS)和催化材料与还原I3 -电解质界面间的传荷电阻(RCt),CZTSe@碳布的RS值为10.07Ωcm2,远远低于理想对电极材料要求的15Ωcm2,如此小的RS值表明CZTSe纳米片与碳布基底间的结合力好。CZTSe@碳布的RCt值为2.28Ωcm2,表明电子在催化材料和电解质间的迁移速度快,且该复合电极的催化性能好。综合考虑,可以得出CZTSe生长在碳布表面可提高电极本身对I3 -的催化还原性能的结论。
实施例2
CZTSe@碳布复合对电极制备过程中,第三步,采用线性扫描曲线功能,电沉积电势为-1.0V,沉积时间为600s,电沉积环境温度控制在22℃,无需搅拌;其余步骤与实施例1相同。
实施例3
CZTSe@碳布复合对电极制备过程中,第三步,采用线性扫描曲线功能,电沉积电势为-1.13V,沉积时间为600s,电沉积环境温度控制在22℃,无需搅拌;其余步骤与实施例1相同。
实施例4
CZTSe@碳布复合对电极制备过程中,第三步,采用线性扫描曲线功能,电沉积电势为-1.20V,沉积时间为600s,电沉积环境温度控制在22℃,无需搅拌;其余步骤与实施例1相同。
实施例5
CZTSe@碳布复合对电极制备过程中,第三步,采用线性扫描曲线功能,电沉积电势为-1.50V,沉积时间为600s,电沉积环境温度控制在22℃,无需搅拌;其余步骤与实施例1相同。
实施例6
CZTSe@碳布复合对电极制备过程中,第三步,采用线性扫描曲线功能,电沉积电势为-1.17V,沉积时间为30s,电沉积环境温度控制在22℃,无需搅拌;其余步骤与实施例1相同。
实施例7
CZTSe@碳布复合对电极制备过程中,第三步,采用线性扫描曲线功能,电沉积电势为-1.17V,沉积时间为300s,电沉积环境温度控制在22℃,无需搅拌;其余步骤与实施例1相同。
实施例8
CZTSe@碳布复合对电极制备过程中,第三步,采用线性扫描曲线功能,电沉积电势为-1.17V,沉积时间为900s,电沉积环境温度控制在22℃,无需搅拌;其余步骤与实施例1相同。
实施例9
CZTSe@碳布复合对电极制备过程中,第三步,采用线性扫描曲线功能,电沉积电势为-1.17V,沉积时间为1200s,电沉积环境温度控制在22℃,无需搅拌;其余步骤与实施例1相同。
实施例10
CZTSe@碳布复合对电极制备过程中,第四步,称取0.5mM硒粉置于聚四氟乙烯内衬中;其余步骤与实施例1相同。
实施例11
CZTSe@碳布复合对电极制备过程中,第四步,称取1mM硒粉置于聚四氟乙烯内衬中;其余步骤与实施例1相同。
实施例12
CZTSe@碳布复合对电极制备过程中,第四步,称取2.5mM硒粉置于聚四氟乙烯内衬中;其余步骤与实施例1相同。
实施例13
CZTSe@碳布复合对电极制备过程中,第四步,称取5mM硒粉置于聚四氟乙烯内衬中;其余步骤与实施例1相同。
实施例14
CZTSe@碳布复合对电极制备过程中,第四步,置于200℃烘箱中溶剂热反应1h;其余步骤与实施例1相同。
实施例15
CZTSe@碳布复合对电极制备过程中,第四步,置于200℃烘箱中溶剂热反应6h;其余步骤与实施例1相同。
实施例16
CZTSe@碳布复合对电极制备过程中,第四步,置于200℃烘箱中溶剂热反应12h;其余步骤与实施例1相同。
实施例17
CZTSe@碳布复合对电极制备过程中,第四步,置于200℃烘箱中溶剂热反应30h;其余步骤与实施例1相同。
实施例18
CZTSe@碳布复合对电极制备过程中,第四步,置于200℃烘箱中溶剂热反应48h;其余步骤与实施例1相同。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下还可以做出若干改进,这些改进也应视为本发明的保护范围。
Claims (4)
1.一种染料敏化太阳能电池对电极的制备方法,其特征在于,包括以下步骤:
(1)将碳布分别置于丙酮和乙醇中超声清洗,碳布的沉积面积控制在1×3cm2;
(2)配制三元铜锌锡镀液;
(3)采用电化学工作站组成的三电极体系,以步骤(1)中清洗好的碳布为工作电极、铂片(3×3cm2)为对电极、饱和甘汞电极为参比电极,保证工作电极与对电极正面相对,同时浸泡插入步骤(2)中的铜锌锡镀液中,进行恒电势电沉积,沉积结束后用蒸馏水和乙醇交替清洗碳布,置于烘箱中干燥,得到CZT/碳布预制电极;
(4)称取0.5-5mM硒粉置于聚四氟乙烯模具的聚四氟乙烯内衬中,放入步骤(3)制得的CZT/碳布预制电极,并固定于聚四氟乙烯模具中,将无水乙醇转移至内衬中,使液体体积达到内衬体积的70%,随后直接将内衬密封于不锈钢反应釜中,200℃下溶剂热反应1-48h,冷却至室温后,得到黑色的产物即为染料敏化太阳能电池对电极。
2.如权利要求1所述的染料敏化太阳能电池对电极的制备方法,其特征在于,步骤(2)中,配制三元铜锌锡镀液的方法:首先称取50mM二水柠檬酸钠,加入去离子水搅拌使其溶解均匀,得到澄清透明溶液,随后依次加入3.5mM五水硫酸铜、20mM一水硫酸锌和2.1mM硫酸亚锡,充分搅拌使其溶解均匀,获得含三种金属离子的澄清蓝色镀液。
3.如权利要求1所述的染料敏化太阳能电池对电极的制备方法,其特征在于,步骤(3)中,恒电势电沉积的的工作参数如下:电势范围为-1.0V至-1.5V,沉积时间为30s至1200s,电沉积环境温度为22℃。
4.如权利要求1或2或3所述的染料敏化太阳能电池对电极的制备方法,其特征在于,步骤(4)中,硒粉的用量为2mM。
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CN112233906B (zh) * | 2020-10-13 | 2021-11-02 | 江苏日御光伏新材料科技有限公司 | 一种基于柔性衬底的光阳极及其制备方法 |
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