CN105970146A - 塔式太阳能光热电站吸热器选择性吸收涂层、其制备方法及吸热器 - Google Patents

塔式太阳能光热电站吸热器选择性吸收涂层、其制备方法及吸热器 Download PDF

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CN105970146A
CN105970146A CN201610334330.3A CN201610334330A CN105970146A CN 105970146 A CN105970146 A CN 105970146A CN 201610334330 A CN201610334330 A CN 201610334330A CN 105970146 A CN105970146 A CN 105970146A
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卢鹏荐
胡涛
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Wuhan Tuocai Technology Co ltd
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Abstract

本发明属于太阳能光热发电技术领域，具体涉及一种塔式太阳能光热电站吸热器选择性吸收涂层、其制备方法及吸热器。选择性吸收涂层包括Mo和Co惨杂的Ni‑Cr尖晶石型氧化物层高吸收底层和Ni‑Cu‑Al2O3高透过低发射表层。选择性吸收涂层的制备方法包括：1)高吸收粉末材料的制备；2)底层涂层的制备；3)Ni‑Cu‑Al2O3溶胶凝胶的制备；4)Ni‑Cu‑Al2O3薄膜的制备。本发明所提供的选择性吸收涂层，在可见光和近红外区域的都具有很高的吸收率，同时具有很低的红外发射率。在高温老化试验和盐雾酸碱试验中，涂层都有很稳定的表现，可以满足塔式吸热器的高温、热循环次数多的恶劣环境。

Description

塔式太阳能光热电站吸热器选择性吸收涂层、其制备方法及吸热器
技术领域
本发明属于太阳能光热发电技术领域，具体涉及一种塔式太阳能光热电站吸热器选择性吸收涂层、其制备方法及吸热器。
背景技术
光热发电是继风电、光伏发电之后新能源领域中可再生能源的发展方向，被列入国家《可再生能源发展“十二五”规划》，中国是世界上最大太阳能热水器生产和使用大国，目前主要为低温应用。新型非真空集热器系统填补国内太阳能光热非真空集热管的市场空白，用于太阳能中高温光热发电。太阳能中高温光热发电被称为工业绿色动力，全国工业中、高温热能市场具有30万亿。
太阳能选择性吸收涂层是太阳能光热利用的核心技术之一，它的发展经历了单层金属材料涂覆到多层材料复合等阶段，限于太阳能吸热涂层的应用要求和技术条件，目前多集中在真空太阳能吸热管领域。但塔式太阳能电站目前也是光热发电的主要技术之一，塔式太阳能吸热器表面的选择性涂层是目前的难题，世界上目前使用的也是美国一家公司的高吸收的涂层，但是仍然存在使用寿命短，发射率高等问题。
发明内容
本发明针对目前塔式光热电站吸热器难以制备选择性吸收涂层或涂层寿命短的问题，本发明提供了一种塔式太阳能光热电站吸热器选择性吸收涂层、其制备方法及吸热器。本发明所提供的塔式太阳能光热电站吸热器选择性吸收涂层，具有多层复合的金属陶瓷结构，底层基于尖晶石复合吸收粉末，用热喷涂制备耐高温吸收涂层，再在外层采用溶胶凝胶的形式制备低发射涂层，通过底层高吸收—表层高透过低发射的多层复合涂层来实现高吸收低发射的高温选择性涂层。
一种塔式太阳能光热电站吸热器选择性吸收涂层，包括高吸收底层和高透过低发射表层，其中，所述高吸收底层为Mo和Co惨杂的Ni-Cr尖晶石型氧化物层，所述高透过低发射表层为Ni-Cu-Al2O3层。
具体的，所述高吸收底层中，Mo和Co的质量比为1:1～2，Mo和Co的总质量与Ni-Cr尖晶石型氧化物的质量比为1:10～15。
具体的，所述高透过低发射表层中，Ni的含量为5～10wt％，Cu的含量为10～25wt％。
具体的，所述高吸收底层的厚度小于等于50微米，所述高透过低发射表层的厚度小于等于150纳米。
本发明还提供了一种塔式太阳能光热电站吸热器选择性吸收涂层的制备方法，包括以下步骤：
1)将Mo粉、Co粉和Ni-Cr尖晶石型氧化物粉末混合，经过球磨和过筛，得到粒度为10～20μm的初混粉末，将所述初混粉末依次经过干燥、成型、造粒和烧成，得到复合粉末。
具体的，步骤1)中，Mo和Co的质量比为1:1～2，Mo和Co的总质量与Ni-Cr尖晶石型氧化物的质量比为1:10～15。
2)对不锈钢底层表面进行喷砂处理，得到洁净和多微孔的不锈钢底层，再通过等离子喷涂将步骤1)得到的复合粉末熔融喷涂到不锈钢底层表面，得到高吸收底层。
3)将异丙醇铝缓慢地加入到80～90℃的去离子水中，高速搅拌至充分溶解后，再依次加入CuCl2、硝酸镍、柠檬酸、正硅酸四乙酯和无水乙醇，制备得到复合溶胶。
4)将步骤2)得到的高吸收底层在步骤3)得到的复合溶胶进行浸渍，浸渍后以0.8～1.2mm/s的速度进行提拉镀膜，先将制得的湿膜在常温下自然干燥，再在110～130℃干燥，最后进行热处理，在高吸收底层上形成作为高透过低发射表层的Ni-Cu-Al2O3薄膜，得到塔式太阳能光热电站吸热器选择性吸收涂层。
具体的，步骤4)中的热处理方法为：在箱式电阻炉中以0.8～1.2℃/min的速率缓慢升温至380～420℃，保温1.5～2.5h以后随炉冷却，形成Ni-Cu-Al2O3薄膜。
具体的，步骤4)中形成的Ni-Cu-Al2O3薄膜中，Ni的含量为5～10wt％，Cu的含量为10～25wt％。
本发明还提供了一种塔式太阳能光热电站吸热器，其设置有本发明所提供的上述塔式太阳能光热电站吸热器选择性吸收涂层。
本发明所提供的选择性吸收涂层，在可见光和近红外区域的都具有很高的吸收率，同时具有很低的红外发射率。在高温老化试验和盐雾酸碱试验中，涂层都有很稳定的表现，可以满足塔式吸热器的高温、热循环次数多的恶劣环境。
附图说明
图1是本发明所提供的制备方法中等离子喷涂后的高吸收底层的形貌图。
具体实施方式
以下对本发明的原理和特征进行描述，所举实施例只用于解释本发明，并非用于限定本发明的范围。
实施例1
在不锈钢基片上采用超音速火焰喷涂制备厚度为25μm的吸收底层，将制备好底层吸收层的不锈钢片缓慢地浸入溶胶凝胶中，浸渍40s以后以1mm/s的速度对其进行提拉镀膜，先让制得的湿膜在常温下自然干燥3h，再使其在120℃干燥60min，最后放入箱式电阻炉中进行热处理，先以1℃/min的速率缓慢升温至400℃，保温2h以后随炉冷却，即制得Ni-Cu-Al2O3薄膜。Mo与Co的质量比为1:2，Mo和Co的总质量与Ni-Cr尖晶石型氧化物的质量比为1:10。Ni-Cu-Al2O3薄膜中，Ni的含量为10wt％，Cu的含量为20wt％。
经分光光度计测试得到吸收率0.90，发射率0.22。
实施例2
在不锈钢基片上采用超音速制备40μm的吸收底层，然后在制备好的溶胶中浸渍40s以后以1mm/s的速度对其进行提拉镀膜，提拉3次，先让制得的湿膜在常温下自然干燥3h，再使其在120℃干燥60min，最后放入箱式电阻炉中进行热处理，先以1.2℃/min的速率缓慢升温至380℃，保温2h以后随炉冷却，即制得Ni-Cu-Al2O3薄膜。Mo与Co的质量比为1:1，Mo和Co的总质量与Ni-Cr尖晶石型氧化物的质量比为1:15。Ni-Cu-Al2O3薄膜中，Ni的含量为10wt％，Cu的含量为15wt％。
经分光光度计测试得到吸收率0.96，发射率0.11。经过XRD分析，全部是Cu尖晶石结构，可以看出吸收层厚度增加，吸收率增加，同时，将提拉次数增加，其发射率也会降低。
实施例3。
在不锈钢基片上采用超音速制备50μm的吸收底层，然后在制备好的溶胶中浸渍40s以后以0.8mm/s的速度对其进行提拉镀膜，提拉4次，先让制得的湿膜在常温下自然干燥3h，再使其在110℃干燥60min，最后放入箱式电阻炉中进行热处理，先以0.8℃/min的速率缓慢升温至420℃，保温2h以后随炉冷却，即制得Ni-Cu-Al2O3薄膜。Mo与Co的质量比为1:1.5，Mo和Co的总质量与Ni-Cr尖晶石型氧化物的质量比为1:12。Ni-Cu-Al2O3薄膜中，Ni的含量为5wt％，Cu的含量为25wt％
经分光光度计测试得到吸收率0.90，发射率0.15。经过XRD分析，全部是Cu尖晶石结构，吸收层厚度增加，吸收率增加，同时，将提拉次数增加，其发射率也会降低。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种塔式太阳能光热电站吸热器选择性吸收涂层，其特征在于：包括高吸收底层和高透过低发射表层，其中，所述高吸收底层为Mo和Co惨杂的Ni-Cr尖晶石型氧化物层，所述高透过低发射表层为Ni-Cu-Al2O3层。
2.根据权利要求1所述的塔式太阳能光热电站吸热器选择性吸收涂层，其特征在于：所述高吸收底层中，Mo和Co的质量比为1:1～2，Mo和Co的总质量与Ni-Cr尖晶石型氧化物的质量比为1:10～15。
3.根据权利要求1所述的塔式太阳能光热电站吸热器选择性吸收涂层，其特征在于：所述高透过低发射表层中，Ni的含量为5～10wt％，Cu的含量为10～25wt％。
4.根据权利要求1所述的塔式太阳能光热电站吸热器选择性吸收涂层，其特征在于：所述高吸收底层的厚度小于等于50微米，所述高透过低发射表层的厚度小于等于150纳米。
5.一种塔式太阳能光热电站吸热器选择性吸收涂层的制备方法，其特征在于，包括以下步骤：
1)将Mo粉、Co粉和Ni-Cr尖晶石型氧化物粉末混合，经过球磨和过筛，得到粒度为10～20μm的初混粉末，将所述初混粉末依次经过干燥、成型、造粒和烧成，得到复合粉末；
2)对不锈钢底层表面进行喷砂处理，得到洁净和多微孔的不锈钢底层，再通过等离子喷涂将步骤1)得到的复合粉末熔融喷涂到不锈钢底层表面，得到高吸收底层；
3)将异丙醇铝缓慢地加入到80～90℃的去离子水中，高速搅拌至充分溶解后，再依次加入CuCl2、硝酸镍、柠檬酸、正硅酸四乙酯和无水乙醇，制备得到复合溶胶；
4)将步骤2)得到的高吸收底层在步骤3)得到的复合溶胶进行浸渍，浸渍后以0.8～1.2mm/s的速度进行提拉镀膜，先将制得的湿膜在常温下自然干燥，再在110～130℃干燥，最后进行热处理，在高吸收底层上形成作为高透过低发射表层的Ni-Cu-Al2O3薄膜，得到塔式太阳能光热电站吸热器选择性吸收涂层。
6.根据权利要求5所述的塔式太阳能光热电站吸热器选择性吸收涂层的制备方法，其特征在于，步骤4)中的热处理方法为：在箱式电阻炉中以0.8～1.2℃/min的速率缓慢升温至380～420℃，保温1.5～2.5h以后随炉冷却，形成Ni-Cu-Al2O3薄膜。
7.根据权利要求5所述的塔式太阳能光热电站吸热器选择性吸收涂层的制备方法，其特征在于：步骤1)中，Mo和Co的质量比为1:1～2，Mo和Co的总质量与Ni-Cr尖晶石型氧化物的质量比为1:10～15。
8.根据权利要求5所述的塔式太阳能光热电站吸热器选择性吸收涂层的制备方法，其特征在于：步骤4)中形成的Ni-Cu-Al2O3薄膜中，Ni的含量为5～10wt％，Cu的含量为10～25wt％。
9.一种根据权利要求5至8任一所述的制备方法制备得到的塔式太阳能光热电站吸热器选择性吸收涂层。
10.一种塔式太阳能光热电站吸热器，其特征在于：设置有权利要求1至4任一所述的塔式太阳能光热电站吸热器选择性吸收涂层或权利要求9所述的塔式太阳能光热电站吸热器选择性吸收涂层。
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