CN110391310B - 一种辐射自降温太阳能电池背板膜及其制备方法 - Google Patents

一种辐射自降温太阳能电池背板膜及其制备方法 Download PDF

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CN110391310B
CN110391310B CN201910694452.7A CN201910694452A CN110391310B CN 110391310 B CN110391310 B CN 110391310B CN 201910694452 A CN201910694452 A CN 201910694452A CN 110391310 B CN110391310 B CN 110391310B
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许仲梓
陆春华
管自生
方亮
倪亚茹
寇佳慧
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Abstract

本发明公开了一种辐射自降温太阳能电池背板膜及其制备方法，该辐射自降温太阳能电池背板膜由底面的绝缘阻隔层、中间粘结层和上表面的8～14μm红外选择性辐射功能层构成；其中其中含氟功能组合物由8～14μm红外选择性辐射纳米功能组合物和含氟聚合物组成，含氟聚合物质量为含氟功能组合物总质量的20％～80％；8～14μm红外选择性辐射纳米功能组合物由纳米二氧化硅、稀土硅酸盐化合物和钼酸盐化合物按照质量比例1:(0.5～2):(0.5～2)组合而成。本发明制备工艺简单，制得的背板膜具有优异的紫外‑可见‑近红外太阳光反射性能、导热性能和红外选择性辐射自降温功能，在降低电池背板温度，提高太阳能电池整体光电转换效率具有巨大的潜力。

Description

一种辐射自降温太阳能电池背板膜及其制备方法
技术领域
本发明属于太阳能电池技术领域，尤其涉及一种辐射自降温太阳能电池背板膜及其制备方法。
背景技术
太阳能电池是一种将太阳能转换为电能的装置，是一种清洁绿色的能源转换技术。由于离不开太阳光的辐照，太阳能电池需要长期暴露在外界自然环境中，光伏组件中电池片易于受到大气环境中的紫外线、氧气、水汽等作用而发生老化。此外，由于太阳光中大部分红外光不能被太阳能电池吸收利用，这些红外光常常会被吸收转化为热，因此，在受自身太阳光光热作用以及处于夏季高温等环境下时，太阳能电池背板低的传热和散热能力会在较大程度上降低电池整体光电转换效率。
纳米改性有机氟材料具有良好的耐候性、耐化学腐蚀、防水汽以及机械性能，因而获得了广泛的应用。目前，我国使用的有机氟膜主要有杜邦公司生产的聚氟乙烯(PVF)Tedlar膜，3M公司生产的THV膜、Honeywell生产的ECTFE膜、Arkema公司生产的Kynar膜，等等，这些有机氟膜大多是以含氟高分子/PMMA/钛白粉等为基础材料制成的白色薄膜。
辐射自降温是地面物体通过红外大气窗口将热量传递至外太空，进而降低自身温度的一种物理机制。在太阳光照条件下，物体表面温度的降低主要与几个方面密切相关：第一，对太阳光能量的吸收，要求物体表面对0.3～2.5μm太阳光要有尽可能高的反射；第二，对大气红外辐射能量的吸收，要求物体表面在非大气红外窗口区对周围环境中的大气红外能量有尽可能低的吸收；第三，通过红外窗口向大气环境中排出红外辐射，要求物体表面对8～14μm的红外光能量具有高的辐射；第四，自然空气下的热对流及热传导。
从目前太阳能电池背板的基础组成来看，背板组成主要包括钛白粉和含氟高分子/PMMA聚合物树脂，由于背板中钛白粉等功能填料在红外光谱区的选择性吸收辐射性能不强，制得的背板难以发挥有效的辐射自降温效果。从现有公开报道来看，辐射自降温材料在夜晚无光照条件下已有很好的辐射降温效果，但是白天光照条件下的降温效果仍未达到使用要求。例如，A.P.Raman(Nature,2014,515,540)和M.M.Hossain等(Adv.Opt.Mater.2015,3,1047)报道了运用纳米光刻蚀/等离子沉积等技术构筑出了辐射自降温性能良好的纳米微尺度结构的辐射降温器，但这类制造工艺复杂、成本高，难以大规模生产应用。Ronggui Yang等(Science，2017，355,1062)报道了利用玻璃微球与聚合物均匀混合并镀上高反射金属膜制成的辐射自降温器，但由于玻璃微球在红外光谱区的选择性吸收辐射性能不强，这种辐射降温器尚未满足应用需求。因此，开发易于大规模低成本制造的选择性辐射自降温太阳能电池背板膜具有重要应用需求。
发明内容
本发明的目的是提供一种能解决现有技术中存在缺陷的辐射自降温太阳能电池背板膜，本发明的另一目的是提供上述辐射自降温太阳能电池背板膜的制备方法。
本发明的技术方案为：一种辐射自降温太阳能电池背板膜，其特征在于依次由绝缘阻隔层、粘结层和8～14μm红外选择性辐射功能层构成；8～14μm红外选择性辐射功能层由柔性高反射膜和含氟功能组合物组成；其中含氟功能组合物由8～14μm红外选择性辐射纳米功能组合物和含氟聚合物组成，含氟聚合物的质量为含氟功能组合物总质量的20％～80％；8～14μm红外选择性辐射纳米功能组合物由纳米二氧化硅、稀土硅酸盐化合物和钼酸盐化合物按照质量比1:(0.5～2):(0.5～2)组合而成，其中稀土硅酸盐化合物组成为SiO2-(0.5～2.0)RE2O3-(0.1～1.0)Na2O，RE为La、Sm、Eu、Gd、Tb、Dy、Er、Tm、Yb、Y或Sc，钼酸盐化合物的化学组成为RMoO4，R为Mg、Ca、Sr或Ba。
上述绝缘阻隔层为纳米蒙脱土或云母改性PET树脂；粘结层为聚氨酯、丙烯酸或环氧树脂粘结层的任意一种。
优选上述绝缘阻隔层厚度介于50～200μm，红外选择性辐射功能层厚度介于25～45μm。
优选所述柔性高反射膜为反射率大于95％的金属铝膜或镀铝聚合物功能膜；厚度介于15～20μm。
优选所述含氟聚合物为聚氟乙烯PVF、聚偏氟乙烯PVDF、聚三氟氯乙烯PCTFE或聚四氟乙烯PTFEDE的任意一种。
上述红外选择性辐射纳米功能组合物中二氧化硅在8～10μm红外光谱范围内具有强选择性吸收/辐射特性(红外辐射吸收系数大于0.8)，稀土硅酸盐化合物在9～12μm红外光谱范围内具有强选择性吸收/辐射特性(红外辐射吸收系数大于0.8)，钼酸盐化合物在10～14μm红外光谱范围内具有强选择性吸收/辐射特性(红外辐射吸收系数大于0.8)。
优选所述的纳米稀土硅酸盐氧化物由以下方法制备得到：根据稀土硅酸盐化合物的化学计量比，准确称取纳米二氧化硅、稀土硝酸盐和硝酸钠，混合分散到乙醇水混合溶液中；在70～80℃水浴搅拌条件下蒸发溶剂得到凝胶；经120～150℃低温预烧处理3～6小时后，再在600～900℃热处理3～12小时得到稀土硅酸盐化合物。
优选所述的纳米钼酸盐化合物由以下方法制备得到：根据钼酸盐化合物的化学计量比，准确称取钼酸铵和碱土金属硝酸盐，溶解到去离子水中；配置质量浓度为5％～10％柠檬酸溶液，搅拌滴加到上述溶液中，调节pH至3.0～4.0，在70～80℃水浴搅拌条件下蒸发溶剂得到凝胶；经120～150℃低温预烧处理3～6小时后，再800～1000℃热处理3～12小时后，即得到钼酸盐化合物。
本发明还提供了上述的一种辐射自降温太阳能电池背板膜的制备方法，其具体步骤如下：
(a)按重量比例，称取一定份数的纳米二氧化硅、稀土硅酸盐化合物、钼酸盐化合物，以及含氟聚合物，一起加入高速混合机中，在80～100℃下搅拌混合10～60分钟，得到含氟功能聚合物预混料；
(b)利用双螺杆挤出机将(a)步骤中得到的含氟功能聚合物预混料制成相应的含氟功能聚合物母粒；
(c)将(b)步骤中制得的含氟功能聚合物母粒加入单螺杆挤出机中，经高温塑化、与柔性高反射金属膜共挤出、双辊冷却、牵引、收卷等工艺过程，制得8～14μm红外选择性辐射功能层薄膜。
(d)运用多层共挤复合工艺，采用粘结剂将(c)步骤中制得的8～14μm红外选择性辐射功能层薄膜与绝缘阻隔层粘接复合起来，即可获得所需的辐射自降温太阳能电池背板膜。
有益效果：
本发明的辐射自降温太阳能电池背板膜，制备工艺简单，不仅具有优异的红外强选择性吸收/辐射功能，而且还具有良好的耐候性、水汽阻隔性、力学性能，在降低电池背板温度提高光电转换效率、延长使用寿命等方面具有巨大的潜在的应用前景。
具体实施方式
为了更好的理解本发明，特例举以下实施例对本发明进行详细阐述，但本发明的内容绝不仅仅限于下面的实施例。
实施例1
所用纳米稀土硅酸盐化合物组成为SiO2-1.8La2O3-0.2Na2O，准确称取所需30克纳米SiO2(市售，50nm)、487.35克La(NO3)3和17克NaNO3，完全溶解、混合乙醇水混合溶液中，水浴70℃搅拌条件下蒸发溶剂得到凝胶，150℃热处理3小时得到稀土硅酸镧预烧粉，700℃热处理12小时得到纳米稀土硅酸镧化合物，平均粒度95nm。
所用纳米钼酸盐化合物组成为MgMoO4，准确称取原料74.15克Mg(NO3)2、98克(NH4)2MoO4，完全溶解混合到去离子水中。配置质量浓度为10％柠檬酸溶液，逐滴加入到上述溶液中，边加边剧烈搅拌，用氨水调节pH至3.0，水浴70℃搅拌条件下蒸发溶剂得到凝胶，150℃热处理6小时得到钼酸镁预烧粉，850℃热处理12小时得到纳米钼酸镁，平均粒度97nm。
所用绝缘阻隔层为市售纳米云母改性PET聚合物，厚度为150μm；所用高反射柔性金属膜为市售镀铝PET膜(15μm)，太阳光反射率为95％；所用含氟聚合物为聚偏氟乙烯(PVDF)，PVDF含氟聚合物占红外辐射功能层固含量的质量分数为60％。
一种辐射自降温太阳能电池背板膜的制备方法，包括以下步骤：
(a)按重量比例1:2:2，称取15份纳米二氧化硅、20份纳米稀土硅酸盐化合物、20份纳米钼酸盐化合物，以及75份PVDF聚合物树脂，一起加入高速混合机中，在100℃高速搅拌30分钟，得到PVDF功能聚合物。
(b)利用双螺杆挤出机将(a)步骤中得到的PVDF功能聚合物预混料制成相应的PVDF功能聚合物母粒；
(c)将(b)步骤中制得的PVDF功能聚合物母粒加入单螺杆挤出机中，经高温塑化、与柔性高反射金属膜共挤出、双辊冷却、牵引、收卷等工艺过程，制得8～14μm红外选择性辐射功能层薄膜(25μm)。
(d)运用多层共挤复合工艺，采用丙烯酸粘结剂将(c)步骤中制得的8～14μm红外选择性辐射功能层薄膜与绝缘阻隔层粘接复合起来，即可获得所需的辐射自降温太阳能电池背板膜，该背板膜在8～14μm红外波长范围的吸收/辐射率最大为0.89。
实施例2
所用纳米稀土硅酸盐化合物组成为SiO2-0.5Y2O3-1.0Na2O，准确称取所需原料30克纳米SiO2(市售，30nm)、137.5克Y(NO3)3和85克NaNO3，完全溶解、混合到乙醇水混合溶液中，水浴75℃搅拌条件下蒸发溶剂得到凝胶，120℃热处理6小时得到稀土硅酸钇预烧粉，800℃热处理6小时得到纳米稀土硅酸钇，平均粒度为120nm。
所用纳米钼酸盐化合物化学式为CaMoO4，准确称取82克Ca(NO3)2、98克(NH4)2MoO4，完全溶解混合到去离子水中。配置质量浓度为5％柠檬酸溶液，逐滴加入到上述溶液中，边加边剧烈搅拌，用氨水调节pH至3.0，水浴80℃搅拌条件下蒸发溶剂得到凝胶，120℃热处理6小时得到钼酸钙预烧粉，1000℃热处理3小时得到纳米钼酸钙，平均粒度为110nm。
所用绝缘阻隔层为市售纳米云母改性PET聚合物，厚度为180μm；所用高反射柔性金属膜为市售铝膜(15μm)，太阳光反射率为97％；所用含氟聚合物为聚四氟乙烯(PTFEDE)，PTFEDE聚合物含氟聚合物占红外辐射功能层固含量的质量分数为50％。
一种辐射自降温太阳能电池背板膜的制备方法，包括以下步骤：
(a)按重量比例1:0.5:2，称取10份纳米二氧化硅、5份纳米稀土硅酸钇、20份纳米钼酸钙，以及35份PTFEDE聚合物树脂，一起加入高速混合机中，在80℃高速搅拌60分钟，得到含氟PTFEDE功能聚合物。
(b)利用双螺杆挤出机将(a)步骤中得到的PTFEDE功能聚合物预混料制成相应的PTFEDE功能聚合物母粒；
(c)将(b)步骤中制得的PVDF含氟功能聚合物母粒加入单螺杆挤出机中，经高温塑化、与柔性高反射金属膜共挤出、双辊冷却、牵引、收卷等工艺过程，制得8～14μm红外选择性辐射功能层薄膜(30μm)。
(d)运用多层共挤复合工艺，采用丙烯酸粘结剂将(c)步骤中制得的8～14μm红外选择性辐射功能层薄膜与绝缘阻隔层粘接复合起来，即可获得所需的辐射自降温太阳能电池背板膜，该背板膜在8～14μm红外波长范围的吸收/辐射率最大为0.86。
实施例3
所用纳米稀土硅酸盐化合物具备以下组成SiO2-1.0Gd2O3-0.5Na2O，准确称取所需30克纳米SiO2(市售，50nm)、343.25克Gd(NO3)3和42.5克NaNO3，完全溶解混合到乙醇水混合溶液中，水浴80℃搅拌条件下蒸发溶剂得到凝胶，120℃热处理6小时得到稀土硅酸钆预烧粉，900℃热处理3小时得到纳米稀土硅酸钆化合物，平均粒度为80nm。
所用纳米钼酸盐化合物化学式为MgMoO4，准确称取74.15克Mg(NO3)2、98克(NH4)2MoO4，完全溶解到去离子水中。配置质量浓度为10％柠檬酸溶液，逐滴加入到上述溶液中，边加边剧烈搅拌，用氨水调节pH至4.0，水浴70℃搅拌条件下蒸发溶剂得到凝胶，150℃热处理3小时得到钼酸镁预烧粉，900℃热处理6小时得到纳米钼酸镁化合物，平均粒径为90nm。
所用绝缘阻隔层为市售绝缘阻隔层为纳米蒙脱土改性PET，厚度为120μm；所用高反射柔性金属膜为市售镀铝PP膜(20μm)，太阳光反射率为95％；所用含氟聚合物为聚氟乙烯PVF，PVF聚合物含氟聚合物占红外辐射功能层固含量的质量分数为30％。
一种辐射自降温太阳能电池背板膜的制备方法，包括以下步骤：
(a)按重量比例1:1:0.5，称取10份纳米二氧化硅、10份纳米稀土硅酸钆化合物、5份纳米钼酸镁化合物，以及10.7份PVF聚合物，一起加入高速混合机中，在80℃高速搅拌40分钟，得到PVF功能聚合物。
(b)利用双螺杆挤出机将(a)步骤中得到的PVF功能聚合物制成相应的高耐候性PVF功能聚合物母粒。
(c)将(b)步骤中制得的PVF含氟聚合物功能母粒加入单螺杆挤出机中，通过高温塑化、与高反射柔性金属铝膜共挤出、双辊冷却、牵引、收卷等工艺过程制得8～14μm红外选择性辐射功能层(40μm)。
(d)采用聚氨酯粘结剂，通过多层共挤复合工艺将(c)步骤中制得的8～14μm红外选择性辐射功能层与蒙脱土改性PET绝缘阻隔层粘结复合起来，即可获得所需的辐射自降温太阳能电池背板膜，该背板膜在8～14μm红外波长范围的吸收/辐射率最大为0.90。

Claims (8)

1.一种辐射自降温太阳能电池背板膜，其特征在于：依次由绝缘阻隔层、粘结层和8～14μm红外选择性辐射功能层构成；其中8～14μm红外选择性辐射功能层由柔性高反射膜和含氟功能组合物组成；其中含氟功能组合物由8～14μm红外选择性辐射纳米功能组合物和含氟聚合物组成，含氟聚合物的质量为含氟功能组合物总质量的20％～80％；8～14μm红外选择性辐射纳米功能组合物由纳米二氧化硅、稀土硅酸盐化合物和钼酸盐化合物按照质量比例1:(0.5～2):(0.5～2)组合而成，其中稀土硅酸盐化合物组成为SiO2-(0.5～2.0)RE2O3-(0.1～1.0)Na2O，RE为La、Sm、Eu、Gd、Tb、Dy、Er、Tm、Yb、Y或Sc，钼酸盐化合物的化学组成为RMoO4，R为Mg、Ca、Sr或Ba。
2.根据权利要求1所述的一种辐射自降温太阳能电池背板膜，其特征在于：绝缘阻隔层为纳米蒙脱土或云母改性PET树脂；粘结层为聚氨酯、丙烯酸或环氧树脂粘结层的任意一种。
3.根据权利要求1所述的一种辐射自降温太阳能电池背板膜，其特征在于：所述绝缘阻隔层厚度介于50～200μm，红外选择性辐射功能层厚度介于25～45μm。
4.根据权利要求1所述的一种辐射自降温太阳能电池背板膜，其特征在于：所述柔性高反射膜为反射率大于95％的金属铝膜或镀铝聚合物功能膜；厚度介于15～20μm。
5.根据权利要求1所述的一种辐射自降温太阳能电池背板膜，其特征在于：所述含氟聚合物为聚氟乙烯PVF、聚偏氟乙烯PVDF、聚三氟氯乙烯PCTFE或聚四氟乙烯PTFEDE的任意一种。
6.根据权利要求1所述的一种辐射自降温太阳能电池背板膜，其特征在于：所述的纳米稀土硅酸盐氧化物由以下方法制备得到：根据稀土硅酸盐化合物的化学计量比，准确称取纳米二氧化硅、稀土硝酸盐和硝酸钠，混合分散到乙醇水混合溶液中；在70～80℃水浴搅拌条件下蒸发溶剂得到凝胶；经120～150℃低温预烧处理3～6小时后，再在600～900℃热处理3～12小时得到稀土硅酸盐化合物。
7.根据权利要求1所述的辐射自降温太阳能电池背板膜，其特征在于：所述的纳米钼酸盐化合物由以下方法制备得到：根据钼酸盐化合物的化学计量比，准确称取钼酸铵和碱土金属硝酸盐，溶解到去离子水中；配置质量浓度为5％～10％柠檬酸溶液，搅拌滴加到上述溶液中，调节pH至3.0～4.0，在70～80℃水浴搅拌条件下蒸发溶剂得到凝胶；经120～150℃低温预烧处理3～6小时后，再800～1000℃热处理3～12小时后，即得到钼酸盐化合物。
8.一种制备如权利要求1所述的辐射自降温太阳能电池背板膜的制备方法，其具体步骤如下：
(a)按重量比例，称取一定份数的纳米二氧化硅、稀土硅酸盐化合物、钼酸盐化合物，以及含氟聚合物，一起加入高速混合机中，在80～100℃下搅拌混合10～60分钟，得到含氟功能组合物预混料；其中纳米二氧化硅、稀土硅酸盐化合物和钼酸盐化合物的质量比例为1:(0.5～2):(0.5～2)；
(b)利用双螺杆挤出机将(a)步骤中得到的含氟功能组合物预混料制成相应的含氟功能组合物母粒；
(c)将(b)步骤中制得的含氟功能组合物母粒加入单螺杆挤出机中，经塑化、与柔性高反射金属膜共挤出、双辊冷却、牵引、收卷工艺过程，制得8～14μm红外选择性辐射功能层薄膜；
(d)运用多层共挤复合工艺，采用粘结剂将(c)步骤中制得的8～14μm红外选择性辐射功能层薄膜与绝缘阻隔层粘接复合起来，即获得所需的辐射自降温太阳能电池背板膜。
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