CN104538499B - 太阳能薄膜材料铜锌锡硫粉体的制备方法 - Google Patents
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- 229910052786 argon Inorganic materials 0.000 claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 11
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 238000005987 sulfurization reaction Methods 0.000 abstract description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
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Abstract
一种制备太阳能薄膜用铜锌锡硫粉体的方法，本发明的原料为铜粉、硫化锌、氧化锡、硫磺，它们的依次摩尔比例为2:1:1:4.5‑5，将它们用湿法分别进行前处理后混合一起再进行超声波搅拌，充分搅拌均匀后抽滤干燥后得到混合均匀的混合粉末，在氩气保护下，在温度为230 oC ～950 oC之间将该混合粉末进行高温烧结反应。将反应完成后的产品冷却后进行粉碎球磨，得到所需铜锌锡硫粉体材料。本发明不仅工艺流程简单，低碳环保，设备要求低，产品成本低，制备十分方便容易，而且提高了产品质量，可规模化生产，解决了一般硫化法制备的CZTS太阳能薄膜中，S 的分布不均匀，存在梯度，即靠近钼（Mo）层处S 含量低的问题。
Description
技术领域
太阳能薄膜材料铜锌锡硫粉体的制备方法，属于太阳能光伏电池材料。
背景技术
太阳能光伏电池是一种将光能转换为电能的器件。一直以来，太阳能光伏器件是使用昂贵的硅(Si) 作为吸光半导体材料进行制作，器件价格非常昂贵。为了让太阳能光伏电池能被广泛接受，就必须做到价格低廉，经济实用。所以世界各国都在开发新型太阳能电池，使用价格低廉的薄膜及吸光半导体材料，比如铜- 铟- 镓-硒薄膜，简称为CIGS；以及铜- 锌- 锡-硫薄膜，简称为CZTS (Cu2ZnSnS4)。CIGS 在薄膜太阳能电池中已开始进行大量生产，但是其中的铟和硒有毒性，而且是稀有资源，价格昂贵。造成CIGS 在商业应用推广中障碍重重。目前最有前景的可替代物是由铜锌锡硫元素构成的四元化合物，它是用锌元素和锡元素代替了铜铟镓硒中的铟元素和镓元素，它具有约1.5eV 的直接能带隙和大于104cm-1 的吸光系数。并且，CZTS 不包括任何稀有金属元素，价格低廉，原料也十分容易获得，制备工艺流程环保，应用前景十分广阔。CZTS薄膜太阳电池由背电极Mo，吸收层CZTS，缓冲层CdS，窗口层i-ZnO和ZAO以及顶电极组成。
目前， CZTS 薄膜所需铜锌锡硫粉体材料制备的主要方法有磁控溅射法、脉冲激光沉积法、沉积金属前驱体再经硫化和溶剂热法。这些方法工艺复杂，各元素成分难以精确控制，而且制备工艺中往往需使用有毒的硫化氢气体，制备成本高。因此，研发新的可规模化生产，工艺简单，成本低廉又环保的铜锌锡硫粉末材料制备方法是十分必要的。
发明内容
本发明的目的是针对光伏太阳能薄膜电池而制备的铜锌锡硫粉体材料，提供一种新的制备方法。原料为铜粉、硫化锌、氧化锡、硫磺，它们的依次摩尔比例为2:1:1:4-5，将它们充分混合后，放入无水乙醇进行超声波搅拌，再进行造粒烘干，在氩气保护下，在温度为350 oC ～1100 oC之间进行分阶段烧结反应。将反应完成后的产品冷却后进行粉碎球磨，得到所需铜锌锡硫粉体材料。具体制备工艺如下：
A：配料
原料为铜粉、硫化锌、氧化锡、硫磺，它们的依次摩尔比例为2:1:1:4-5，
B：前处理
铜粉、硫化锌、氧化锡、硫磺分别进行过筛除杂。
C：混料
铜粉、硫化锌、氧化锡、硫磺，在空气气氛下或惰性气体气氛下机械搅拌30 ～100 分钟，进行充分混合。
D:造粒
在充分混合好的混合物中加入由聚乙烯醇缩丁醛和无水乙醇配制的助剂溶液，该助剂溶液的浓度在1%-6%之间，用超声波进行充分搅拌20 ～60 分钟，送入造粒机中进行造粒。
E：烘干
将造好粒的混合物放入烘干机中在氩气保护下进行烘干，温度在60 oC ～100 oC之间。
F：反应炉反应
装舟，进炉，进行氩气保护，在氩气保护下加热至350 oC ～1100 oC之间进行高温烧结，烧结温度分低中高三个温度区，低温区350～480℃，中温区500～880℃，高温区900～1100℃，反应后保温3 ～ 10小时。
G： 磨料
将冷却后的反应物进行粉碎磨料，直到粒径小于100微米。
H： 振动筛分级
将磨料好的产品按粒径大小进行振动筛分得到不同粒级的铜锌锡硫粉体材料。
本发明方法不仅工艺流程简单，低碳环保，设备要求低，产品成本低，制备十分方便容易，而且提高了产品质量，可规模化生产，解决了一般硫化法制备的CZTS太阳能薄膜中，S 的分布不均匀，存在梯度 ，即靠近钼（Mo）层处S 含量低的问题，同时使产品粒度更均匀，性能更稳定可靠，生产效率更高。所生产的铜锌锡硫粉体材料完全可以满足光伏太阳能薄膜电池的需要，同时也可以制备成各种规格的靶材和块材。产品特别适合于大规模工业自动化生产，应用前景十分广阔。
具体实施方式
实施例1
将铜粉、硫化锌、氧化锡、硫磺按摩尔比2∶ 1 ∶ 1 ∶ 4.2 充分混合均匀，加入浓度为1%的聚乙烯醇缩丁醛和无水乙醇配制的助剂溶液，超声波搅拌，造粒，在氩气保护下送入烘干箱中烘干。然后将烘干好的混合物再放入反应炉中，通入氩气，烧结低温区为400℃，中温区500℃，高温区1100℃，分别烧结1小时，2小时和2小时，保温3小时，等所得样品冷却后，取出研磨直到粒径小于100微米，振动筛分级后得到不同粒级的得到铜锌锡硫粉体材料。
实施例2
将铜粉、硫化锌、氧化锡、硫磺按摩尔比2∶ 1 ∶ 1 ∶ 4.5充分混合均匀，加入浓度为3%的聚乙烯醇缩丁醛和无水乙醇配制的助剂溶液，超声波搅拌，造粒，在氩气保护下送入烘干箱中烘干。然后将烘干好的混合物再放入反应炉中，通入氩气，烧结低温区为350℃，中温区850℃，高温区1000℃，分别烧结1小时，2小时和3小时，保温6小时，等所得样品冷却后，取出研磨直到粒径小于100微米，振动筛分级后得到不同粒级的铜锌锡硫粉体材料。
实施例3
将铜粉、硫化锌、氧化锡、硫磺按摩尔比2∶ 1 ∶ 1 ∶ 5充分混合均匀，加入浓度为5%的聚乙烯醇缩丁醛和无水乙醇配制的助剂溶液，超声波搅拌，造粒，在氩气保护下送入烘干箱中烘干。然后将烘干好的混合物再放入反应炉中，通入氮气，烧结低温区为450℃，中温区700℃，高温区1050℃，分别烧结1小时，1.5小时和2.5小时后保温8 小时，等所得样品冷却后，取出研磨直到粒径小于100微米，振动筛分级后得到不同粒级的得到铜锌锡硫粉体材料。
Claims (2)
1.太阳能薄膜材料铜锌锡硫粉体的制备方法，其特征在于包括以下步骤：
A：配料
按铜粉、硫化锌、氧化锡和硫磺的摩尔比为2:1:1:4-5进行配料；
B：前处理
铜粉、硫化锌、氧化锡、硫磺分别进行过筛除杂；
C：混料
铜粉、硫化锌、氧化锡、硫磺，在空气气氛下或惰性气体气氛下机械搅拌30 ～100 分钟，进行充分混合；
D:造粒
在充分混合好的混合物中加入由聚乙烯醇缩丁醛和无水乙醇配制的助剂溶液，该助剂溶液的浓度在1%-6%之间，用超声波进行充分搅拌20
～60 分钟，送入造粒机中进行造粒；
E：烘干
将造好粒的混合物放入烘干机中在氩气保护下进行烘干，温度在60 oC ～100 oC之间；
F：反应炉反应
将烘干好的物料装舟，送进反应炉，在氩气保护下加热至350 oC ～1100 oC之间进行高温烧结，烧结分低中高三个温度区，低温区350～480℃，中温区500～880℃，高温区900～1100℃，反应后保温3 ～ 10小时；
G： 磨料
将冷却后的反应物进行粉碎磨料，直到粒径小于100微米；
H： 振动筛分级
将磨料好的产品按粒径大小进行振动筛分得到不同粒级的铜锌锡硫粉体材料。
2.如权利要求1所述的太阳能薄膜材料铜锌锡硫粉体的制备方法，其特征在于：C步骤所述的惰性气体气氛为氩气。
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| CN102689920A (zh) * | 2012-06-20 | 2012-09-26 | 上海大学 | 一种溶剂热合成铜锌锡硫材料的方法 |
| CN103373741A (zh) * | 2012-04-13 | 2013-10-30 | 河南师范大学 | 一种制备铜锌锡硫粉体的方法 |
| CN104241447A (zh) * | 2014-09-09 | 2014-12-24 | 电子科技大学 | 一种铜锌锡硫薄膜材料的制备方法 |
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| CN103373741A (zh) * | 2012-04-13 | 2013-10-30 | 河南师范大学 | 一种制备铜锌锡硫粉体的方法 |
| CN102689920A (zh) * | 2012-06-20 | 2012-09-26 | 上海大学 | 一种溶剂热合成铜锌锡硫材料的方法 |
| CN104241447A (zh) * | 2014-09-09 | 2014-12-24 | 电子科技大学 | 一种铜锌锡硫薄膜材料的制备方法 |
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