CN108512486A - 一种柔性光电热复合电池 - Google Patents
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- H—ELECTRICITY
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- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03926—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate comprising a flexible substrate
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Abstract
本发明涉及一种柔性光电热复合电池，由太阳能电池、热电电池、柔性衬底组成，太阳能电池和热电电池分别在柔性衬底两侧，通过柔性衬底组合在一起。本发明所提供的技术方案通过在柔性的光伏电池上复合热电电池，除了利用太阳光的光伏发电，可以利用太阳光的热辐射进行发电对发电能力进行补充，可以提高太阳光发电的效率。本发明所涉及的复合电池，综合了太阳能电池和热电电池的优点，采用柔性材料，得到不易破碎、可折叠、可弯曲、质量轻、便于运输和高性能的电池。
Description
技术领域
本发明涉及一种复合电池，具体涉及一种光电转换电池和热电转换电池的光电热复合电池。
背景技术
能源是整个世界发展和经济发展的原动力，但是随着社会的发展和化石能源的使用，随之带来了能源短缺、过度使用能源等一系列无法回避的环境污染，人类生存和发展必须解决这些问题。太阳能是用之不尽，取之不竭的能源，如果能从太阳能获得电力，将造福人类。
光电转换电池便是从太阳能获取能量的途径之一，太阳光照在半导体p-n结上，形成新的空穴-电子对，在p-n结内建电场的作用下，空穴由n区流向p区，电子由p区流向n区，接通电路后就形成电流。这就是光电效应太阳能电池的工作原理。而热电转换电池是通过塞贝克效应(Seebeck effect)实现热能对电能的转换。光伏发电会伴随着大量的太阳热能的辐射，在利用光伏发电的同时能再利用到热能进行发电，这将提高太阳发电的效率。
在现有太阳电池研造中，基体多选用玻璃、陶瓷等刚性材质，整个电池质量沉重，限制了其用途。
发明内容
本发明针对上述刚性材质带来的太阳能电池的一系列问题，本发明提供一种柔性光电热复合电池。
为了实现上述目的，本发明提供了采用下述技术方案：
优选的，所述复合电池依次由太阳能电池、柔性衬底和热电电池叠加而成，所述太阳能电池和热电电池分别位于所述柔性衬底的两侧。
优选的，所述太阳能电池依次由减反层、透明导电层、过渡层、吸收层n(p)、吸收层p(n)和底电极叠加而成；所述减反层一侧设置电极t；所述底电极与所述柔性衬底连接。
优选的，所述太阳能电池的厚度为1纳米～500微米；所述热电电池的厚度为1nm～500um；所述柔性衬底的厚度为1毫米～100毫米。
优选的，所述热电电池两侧由外至内依次设有绝缘层、电极r和成对组成的热电材料p(n)、n(p)；所述电极r间隔对称设置；所述热电材料p(n)和热电材料n(p)分别与所述电极r垂直连接。
优选的，所述吸收层n(p)和吸收层p(n)为晶硅、微晶硅、纳米晶硅、铜铟硒、铜铟镓硒、铜铟镓硒硫、铜锌锡硫和碲化镉中的一种。
优选的，所述透明导电层7为掺铝氧化锌或掺氟氧化锡制得；过渡层9的材料为二氧化钛。
优选的，所述热电材料p(n)和热电材料n(p)为Bi2Te3、Bi2Se3、Sb2Te3、PbTe、Zn4Sb3、ZnSb、CoSb3中的一种。
优选的，所述柔性衬底的材料为不锈钢、钛、铝、镍、锌、钼、铬、聚对苯二甲酸二乙酯、聚萘二酸乙二醇酯、聚酰亚胺中的一种。
优选的，所述复合电池的弯曲角度为0到360°。
与最接近的现有技术比，本发明提供的技术方案具有如下有益效果：
(1)本发明所提供的技术方案通过在柔性的光伏电池上复合热电电池，除了利用太阳光的光伏发电，还可以利用太阳光的热辐射进行发电对发电能力进行补充，可以提高太阳光发电的效率。
(2)本发明技术方案中的耐高温柔性衬底微晶硅薄膜的最高薄膜沉积温度可达350～400℃，利用本发明微晶硅薄膜制得的太阳能电池暗电导率达到2.5×10-5～2.8×10-5S/cm，光学带隙为1.7～1.9eV，光电转换效率达到6.05～6.07％，比刚性衬底微晶硅薄膜太阳能电池的转换率高出55～57％
(3)本发明所涉及的复合电池，综合了太阳能电池和热电电池的优点，采用柔性材料，得到不易破碎、可折叠、可弯曲、质量轻、便于运输和高性能的电池。
附图说明
图1是本发明提供的复合电池结构示意图。
具体实施方式
下面将结合本发明实施例和附图1，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
术语“间隔对称设置”为同层的电极r间隔设置；平行设置的层间的电极r通过所述热电材料p(n)或热电材料n(p)连接；术语“对称”是所述电极r层相对于所述热电材料p(n)和热电材料n(p)层而言的。如图1所示，所述太阳能电池由减反层、透明导电层、过渡层、吸收层n(p)、吸收层p(n)和底电极依次叠加而成；所述减反层一侧设置电极t；所述底电极与所述柔性衬底连接。所述柔性衬底的另一侧设有片式热电电池，该片式热电电池两侧由外至内依次设有绝缘层、电极r和成对组成的热电材料p(n)、n(p)；所述电极r间隔对称设置；所述热电材料p(n)和热电材料n(p)的两端分别与所述电极r垂直连接。
太阳光通过减反层照射到柔性太阳能电池内部，经光伏效应将光能转换成电能，底电极和电极t收集电流。另外，太阳光的热能以辐射方式通过太阳能电池和柔性衬底传递到热电电池，使靠近柔性衬底区域的电极r成为高温区，在具有塞贝克效应(Seebeckeffect)的热电材料p(n)和热电材料n(p)内部发生电子的流动，通过电极r收集电流。
本发明提供的柔性太阳能电池中，吸收层p(n)、吸收层n(p)为晶硅(α-Si)、微晶硅(μ-Si)、纳米晶硅(nc-Si)、铜铟硒(CIS)、铜铟镓硒(CIGS)、铜铟镓硒硫(CIGSS)、铜锌锡硫(CZTS)或碲化镉(CdS)。热电材料p(n)、热电材料n(p)为Bi2Te3、Bi2Se3、Sb2Te3、PbTe、Zn4Sb3、ZnSb或CoSb3。
本发明提供的所述柔性太阳能电池中所述透明导电层7为掺铝氧化锌或掺氟氧化锡制得；过渡层9的材料为二氧化钛。
吸收层的材料和热电材料在器件制备时均需要退火，吸收层p(n)、吸收层n(p)的退火工艺中一般有反应气体，所以在磁控溅射或者蒸镀方式制备的吸收层p(n)和吸收层n(p)退火后再通过分子束外延MBE、金属有机化学气相沉积MOCVD、蒸镀和磁控溅射后在对热电材料p(n)和热电材料n(p)退火。
磁控溅射采用直流溅射，溅射气压：0.3-1.0Pa，溅射功率密度：2～5W/cm2，基片温度：150-450℃；蒸镀方式采用高真空热蒸发，基片温度：150～450℃；分子束外延MBE利用超高真空，基片温度：150-350℃；金属有机化学气相沉积MOCVD采用三甲基铋、二乙基锌、单质Te，Se作为反应源，基片温度：150～450℃。
柔性衬底材料选用金属材料不锈钢、钛、铝、镍、锌、钼、铬、氧化锡锑，或者有机聚合物聚对苯二甲酸二乙酯(PET)、聚萘二酸乙二醇酯(PEN)或聚酰亚胺(PI)。
柔性衬底材料制备如下：于高温反应釜中加入500g聚奈二甲酸乙二醇酯和8g氧化锡锑粉末，加热至400℃物料融化后搅拌混合均匀；用涂布机将混匀后的物料均匀的涂布在1m×1m的玻璃板表面，涂布厚度为1mm，涂布完成后将玻璃板移入50℃下的烘箱中干燥过夜干燥，揭膜得到自制耐高温柔性衬底，备用；将上述制得的高温柔性衬底裁剪成3cm×3cm的小块，分别用丙醇、无水乙醇和去离子水超声清洗5次，其中超声功率为200W，每次清洗时间为10min，去除衬底表面杂质；将清洗完的衬底用氮气吹干后放入薄膜沉积装置的沉积腔室内的基片台上，用真空泵抽真空至10Pa，达到预定压力后再打开分子泵抽本底真空至2×10-3Pa，同时对基片台加热至350℃；当基片台达到预定温度后，向沉积腔室内以20mL/min的速率通入甲硅烷和氢气的混合气，其中甲硅烷和氢气的体积比为1:9，持续通气直至腔室内压力达到200Pa，打开沉积装置的射频电源，开始沉积薄膜处理，其中射频频率为50MHz；待薄膜沉积结束，腔室内温度冷却至室温后，用氮气对混合气通气管路进行清洗5次，去除残余的混合气体，最后取出柔性衬底微晶硅薄膜即可。
所述薄膜沉积装置采用射频多孔空心阴极放电，其中用于放电的大孔直径为2mm，孔深10mm，用于通气的小孔直径为0.5mm，孔深为1mm。
以上实施例仅用以说明本发明的技术方案而非对其限制，尽管参照上述实施例对本发明进行了详细的说明，所属领域的普通技术人员依然可以对本发明的具体实施方式进行修改或者等同替换，而这些未脱离本发明精神和范围的任何修改或者等同替换，其均在申请待批的本发明的权利要求保护范围之内。
Claims (12)
1.一种柔性光电热复合电池，其特征在于，所述复合电池由太阳能电池、柔性衬底和热电电池依次叠加而成。
2.根据权利要求1所述的一种柔性光电热复合电池，其特征在于，所述太阳能电池由减反层、透明导电层、过渡层、吸收层n(p)、吸收层p(n)和底电极依次叠加而成；所述减反层一侧设置电极t；所述底电极与所述柔性衬底连接。
3.根据权利要求1或2所述的一种柔性光电热复合电池，其特征在于，所述太阳能电池的厚度为1纳米～500微米。
4.根据权利要求1所述的一种柔性光电热复合电池，其特征在于，所述热电电池两侧由外至内依次设有绝缘层、电极r和成对组成的热电材料p(n)、n(p)；所述电极r间隔对称设置；所述热电材料p(n)和热电材料n(p)的两端分别与所述电极r垂直连接。
5.根据权利要求1或4所述的一种柔性光电热复合电池，其特征在于，所述热电电池的厚度为1nm～500um。
6.根据权利要求1所述的一种柔性光电热复合电池，其特征在于，所述柔性衬底的厚度为1毫米～100毫米。
7.根据权利要求2所述的一种柔性光电热复合电池，其特征在于，所述吸收层n(p)和吸收层p(n)为从晶硅、微晶硅、纳米晶硅、铜铟硒、铜铟镓硒、铜铟镓硒硫、铜锌锡硫和碲化镉中的一种。
8.根据权利要求2所述的一种柔性光电热复合电池，其特征在于，所述透明导电层7为掺铝氧化锌或掺氟氧化锡制得。
9.根据权利要求2所述的一种柔性光电热复合电池，其特征在于，过渡层9的材料为二氧化钛。
10.根据权利要求4所述的一种柔性光电热复合电池，其特征在于，所述热电材料p(n)和热电材料n(p)为Bi2Te3、Bi2Se3、Sb2Te3、PbTe、Zn4Sb3、ZnSb或CoSb3。
11.根据权利要求1所述的一种柔性光电热复合电池，其特征在于，所述柔性衬底的材料为不锈钢、钛、铝、镍、锌、钼、铬、聚对苯二甲酸二乙酯、聚萘二酸乙二醇酯或聚酰亚胺。
12.根据权利要求1所述的一种柔性光电热复合电池，其特征在于，所述复合电池的弯曲角度为0到360°。
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