CN109037397A - 一种减反射膜的制备方法及叠层太阳电池 - Google Patents
一种减反射膜的制备方法及叠层太阳电池 Download PDFInfo
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Abstract
一种减反射膜的制备方法及叠层太阳电池。所述减反射膜的制备包括:在衬底上制备绒度结构;在绒度结构表面均匀涂布一层固化胶;对固化胶进行固化处理;将绒度结构衬底与固化胶分离,得到具有绒度结构的减反射膜。该减反射膜可用于叠层太阳电池的制备中。可有效降低叠层电池的反射损失,增加光吸收,提高电池整体的光谱响应,并最终提高器件的综合输出性能;制备工艺简单,成本低廉,可重复利用,并且适用于大面积制备和生产;器件制作成本几乎没有增加;大大降低了叠层电池设计中引入衬底绒度结构的实施难度,并且绒度调控的可操作性得以增强,具有较强的应用普适性。
Description
技术领域
本发明属于太阳电池技术领域,具体涉及一种减反射膜的制备方法及叠层太阳电池。
背景技术
增效降本一直是太阳电池行业发展中的核心关键问题。为了实现太阳光的有效利用,增加光电转换效率,人们提出构建多结叠层太阳电池来拓宽光谱利用范围。它是将太阳光光谱分成连续的若干部分,使得波长最短的太阳光被最宽带隙顶电池利用,波长较长的太阳光能够透射通过顶部电池让较窄禁带宽度的底部电池利用,以最大限度地将光能转换为电能。
叠层电池的结构往往较为复杂,对制作工艺和材料的要求较高,加之需要考虑到各功能层物理厚度等方面的限制,很难在叠层电池器件中引入陷光结构。例如,以晶硅材料作为叠层电池中的底电池时,平面晶硅材料的反射率约35%,导致较高的光损失。若对硅子电池所用的衬底进行制绒,对接下来各功能层的制备将提出更苛刻的要求,器件制作的成本也将大幅提高。此外,不同叠层电池中,各子电池的光谱分配不同,需要不同的陷光结构设计,而叠层电池中引入不同绒度结构时,极易导致顶、底电池工艺不兼容,增加器件实现难度,提高电池成本。另一方面,对于有机、无机子电池组成的叠层电池,稳定性差,对外界环境中的水、汽、颗粒等较为敏感,对电池的封装要求较高。
综上,现有叠层太阳电池存在如下不足:
(1)叠层电池中各功能层较多,加之物理厚度限制,在器件内引入陷光结构较为困难,是造成其光谱利用不充分的一个重要原因;
(2)叠层电池制作工艺复杂,即使能对部分子电池(如硅电池)进行表面制绒,也将严重增加工艺复杂程度和器件制作成本;
(3)叠层电池中引入不同绒度结构的难度较高,极易导致顶、底电池工艺不兼容;
(4)当叠层电池以有机电池为顶电池时,稳定性差,太阳电池常用的增透减反膜功能单一,对电池的封装要求较高。
发明内容
本发明目的是克服现有技术存在的上述不足,提供一种减反射膜的制备方法及叠层太阳电池。本发明采取从外部引入具有绒度结构的减反射膜的方法,在不增加叠层电池器件制作工艺复杂性的基础上,增加各子电池的光谱响应,从而提升叠层电池器件的整体输出性能。
本发明的技术方案
一种减反射膜的制备方法,具体包括步骤如下:
S1:在衬底上制备绒度结构;
所述衬底为:硅片、玻璃、铝箔、铜箔、不锈钢板、PET、PEN或PDMS;所述绒度结构为周期性阵列结构或非周期性随机结构;所述绒度结构具体为:线状、柱状、碗状、金字塔状、花瓣状或羽翼状中的一种或两种以上的任意组合;所述绒度结构的微观尺寸为1nm-100μm,优选为1μm-10μm。
绒度结构的设计依据不同电池的设计需求而定。
S2:在绒度结构表面均匀涂布一层固化胶;
所述固化胶为:透明硅胶、透明灌封胶、透明水晶胶或紫外固化胶;所述涂布方法为:喷涂法、点胶机涂布法、旋涂法、刮涂法、狭缝涂布法、喷墨涂布法、倾倒涂布法、铸模涂布法、网版印刷法、胶版印刷法或凹版印刷法;所述固化胶的厚度为0.05-5mm,优选为0.05-2mm;进一步优选为0.05-1mm。
所述固化胶为PDMS和固化剂以10:1体积比混合后组成。
所述固化剂为普通市售产品,一般包括:乙烯基三胺、氨乙基哌嗪、二氨基环乙烷、异佛尔酮二胺、亚甲基双环乙烷胺、乙二胺、二乙烯三胺、三乙烯四胺、四乙烯五胺、多乙烯多胺、二丙烯三胺、二甲胺基丙胺、二乙胺基丙胺、三甲基六亚甲基二胺、二乙基三胺、乙二胺改性物AMINE248、乙二胺加合物、乙二胺、三甲基乙二胺、二乙胺、间苯二胺、间苯二甲胺、二氨基二苯基甲烷、二氨基二苯基砜、间氨基甲胺、联苯胺、氯邻苯二胺、苯二甲胺三聚体、苯二甲胺三聚体衍生物、双苄胺基醚、偏苯二胺、亚甲基双苯二胺、酰胺基胺类、双氰胺中的一种或两种以上的任意组合。
所述步骤S2中固化胶也可以由固化引发剂和助剂组成,为透明聚合物型胶质液体和/或透明非聚合物型胶质液体,所述非聚合物型胶质液体选自金属皂、金属络合物、金属醇盐、卤代硅烷类、2-烷氧基乙醇、β-二酮及烷基醋酸酯,或其组合。
所述的涂布在可盛放衬底的器皿中进行,器皿材质为PET、PEN、玻璃、铝箔、铜箔、不锈钢板、聚四氟乙烯;此外,涂布时通过控制固化胶前驱体溶液的使用剂量,来控制最终固化胶的厚度。
所述涂布固化胶之前还包括对绒度结构表面进行处理,所述表面处理为:去离子水清洗、盐酸溶液清洗、氢氟酸溶液清洗、RCA清洗、紫外光处理、可见光处理或氢等离子体处理中的一种或两种以上的任意组合,处理时间10秒-30分钟,优选为0.5-5分钟。
这一步骤的目的在于利于后续步骤的固化及固化胶与衬底的分离,同时形成表面缺陷较少的绒度表面,减少陷光损失。
S3:对固化胶进行固化处理;
所述的进行固化处理之前还包括:抽真空静置5-60分钟,优选为静置10-30分钟,气压-100-100kPa,优选为0-10kPa。
这一步的目的是使衬底与固化胶紧密接触,及排除固化胶中的气泡。
所述的固化处理条件为:采用热固化时,气压-100-100kPa,优选为0-10kPa;温度20-200℃,优选为50-120℃,进一步优选为70-100℃;时间10分钟-24小时,优选为0.5-15小时,进一步优选为1-8小时;或者,采用光源固化时,处理时间0.5分钟-24小时,优选为1分钟-6小时,进一步优选为1-60分钟,所述光源为:点光源、脉冲光源、紫外灯或高密度灯。
采用热固化时的一个优选条件为:首先在80-200℃下处理10-30分钟,然后在20-80℃条件下处理1-8小时。这样的处理有利于固化后固化胶与衬底的分离,同时利于改善减反射膜在叠层电池应用时,其与顶电池透明电极间的接触,避免造成由于折射率不匹配而导致引入新的光学损耗。
S4:将绒度结构衬底与固化胶分离,得到具有绒度结构的减反射膜。
所述步骤S4之后,还包括对减反射膜进行表面处理,所述表面处理为:去离子水清洗、乙醇清洗、异丙醇清洗、乙二醇清洗、聚乙二醇清洗、盐酸溶液清洗、氢氟酸溶液清洗、RCA清洗、紫外光处理、可见光处理或氢等离子体处理中的一种或两种以上的任意组合,处理时间10秒-30分钟,优选为0.5-5分钟;其中的液体处理步骤优选在超声振荡及10-50℃条件下进行。
这一步骤的目的在于去除表面粘污,同时使其应用于叠层电池时,减反射膜与顶电池的透明电极形成良好接触,避免造成接触面处的光学损失。
本发明同时提供了上述方法制备的减反射膜在制备叠层太阳电池中的应用。
一种叠层太阳电池,所述叠层太阳电池包括由隧穿结连接的n个子电池,n为大于等于1的整数,其中:n个子电池中,顶电池受光面的透明电极上方包括上述方法制备的减反射膜;优选绒面为受光面。
n个子电池均选自但不限于:GaInP,GaInAs,GaAs,Ge,AlGaInP,AlGaInAl,InGaN,CIGS,CZTS,CdTe,CdS,CdSe,SbS,CdSSe,钙钛矿,晶体硅,硅量子点,非晶硅,或微晶硅。
一种钙钛矿/硅叠层太阳电池,所述叠层太阳电池自下而上依次包括:(P1)硅异质结底电池:金属背电极/n型硅薄膜/本征钝化层/n型晶硅衬底/本征钝化层/p型硅薄膜;(P2)隧穿结:TCO或掺杂硅薄膜层;(P3)钙钛矿顶电池:ETL/钙钛矿/HTL;(P4)透明电极TCO,及正面金属电极;(P5)如上述方法制备的减反射膜;优选减反射膜的绒面为受光面。
本发明的优点和有益效果:
(1)有效降低叠层电池的反射损失,增加光吸收,提高电池整体的光谱响应,并最终提高器件的综合输出性能;
(2)所采用的减反射膜为湿法制备,工艺简单,成本低廉,可重复利用,并且适用于大面积制备和生产;
(3)在基本不增加叠层电池工艺复杂程度的基础上实现,器件制作成本几乎没有增加,本发明所得到的减反射膜还可直接应用于现有已封装完成后的电池器件或组件;
(4)大大降低了叠层电池设计中引入衬底绒度结构的实施难度,并且绒度调控的可操作性得以增强,具有较强的应用普适性;
(5)稳定性好,助益封装,对尤其是以有机电池为顶电池的叠层电池,可有效增加器件稳定性,降低电池封装要求。
附图说明
图1是以随机金字塔绒度结构为例的透明减反膜的制备流程示意图。
图2是一种叠层太阳电池结构示意图。
图3是一种钙钛矿/硅叠层太阳电池结构示意图。
图4是实施例1所制备的增透减反膜的绒度因子曲线(A)及积分反射曲线(B)。
图5是实施例1所制备的叠层电池的外量子效率曲线(使用减反射膜前后对比)。
具体实施方式
本发明实施例中具体表征方式及所采用的设备型号包括:光学积分透过(TT)、平面透过(TD)、积分反射等数据,采用Cary5000型紫外-可见-近红外分光光度计测得,绒度因子由(TT-TD)/TT*100%计算求得,表征薄膜对光的散射能力;电池的外量子效率(EQE)为入射光子与电池收集的载流子对的比值,由QEX10型号的外量子效率(QE)测试系统测试,并由Jph(V)=e∫∫wEQE(λ,V)f(λ)dλ直接给出由积分电流密度,用以评估(子)电池的光谱响应情况;电池J-V测试在室温25℃,模拟光源AM1.5、功率密度为100mW/cm2的太阳模拟器下测试。
实施例1:
选取n型单晶硅衬底,在高温碱溶液中,以IPA为添加剂,采用各向异向腐蚀的方法,制备随机金字塔绒度结构表面,尺寸1-3μm;对衬底绒度结构表面采用3%HF溶液浸泡1分钟;采用刮涂法,在衬底表面涂布一层厚度为1mm的市售美国道康宁PDMS固化胶;放入真空腔室,抽真空至0kPa,静置30分钟;而后在80℃恒温条件下静置12小时,冲腔降温至室温后取出;然后将固化胶与衬底分离,得到具有绒度结构的固化胶,并将其在30℃下用去离子水超声振荡2分钟;取出用氮气枪吹干后,将其做为减反射膜,应用于钙钛矿/硅叠层太阳电池中,对电池进行QE和JV测试。
如附图4,通过对制得的减反射膜进行透过和反射测试,得到所制备的减反射膜的绒度因子在550nm,800nm,1100nm处分别达90.14%,82.39%,70.73%,其在300-1200nm波段范围内的平均积分反射率为6.20%,所制备减反射膜的光学性能优于一般的透明导电薄膜(TCO)。将所制备减反射膜应用于钙钛矿/硅叠层太阳电池,电池在300-1200nm波段范围内的光响应情况得到明显提升,电池的外量子效率曲线如附图5所示,电池的顶电池积分电流密度由15.61mA/cm2提升至16.74mA/cm2,底电池积分电流密度由13.88mA/cm2提升至15.26mA/cm2,叠层电池的器件效率由18.25%提升至20.06%;电池的QE积分电流密度和器件效率的提升幅度分别为1.38mA/cm2和9.02%。
实施例2:
选取n型单晶硅衬底,在高温碱溶液中,以IPA为添加剂,采用各向异向腐蚀的方法,制备随机金字塔绒度结构表面,尺寸5-10μm;采用旋涂法,在衬底表面涂布一层厚度为0.1mm的PDMS固化胶;放入真空腔室,抽真空至-1kPa,静置5分钟;而后在120度恒温条件下静置6小时,冲腔降温至室温后取出;然后将固化胶与衬底分离,得到具有绒度结构的固化胶;将其做为减反射膜,应用于钙钛矿/硅叠层太阳电池中,对电池进行QE和JV测试。
通过对制得的减反射膜进行透过和反射测试,得到所制务薄膜的绒度因子在550nm,800nm,1100nm处分别达98.56%,98.17%,97.64%,其在300-1200nm波段范围内的平均积分反射率为5.46%,通过与实施例1相比,所制备的减反射膜的光学性能可通过调节绒度结构尺寸来调控,这样便可增加对器件性能调控的灵活性;所述减反射膜的使用不增加叠层电池制作的工艺复杂性,简便易行,且具有应用范围方面的普适性。将实施例2所制备减反射膜应用于钙钛矿/硅叠层太阳电池,电池的顶电池积分电流密度由15.56mA/cm2提升至16.65mA/cm2,底电池积分电流密度由14.79mA/cm2提升至15.9mA/cm2,叠层电池的器件效率由19.63%提升至21.10%;电池的QE积分电流密度和器件效率的提升幅度分别为1.11mA/cm2和6.97%。
实施例3:
选取玻璃为衬底,以氢氟酸腐蚀的方法,制备随机纳米结构绒度表面,尺寸10-200nm;采用倾倒涂布法,在衬底表面涂布一层厚度为2mm的PDMS固化胶;放入真空腔室,抽真空至0.1kPa,静置1小时;而后在室温静置24小时,冲腔后取出;然后将固化胶与衬底分离,得到具有绒度结构的固化胶;将其做为减反射膜,应用于钙钛矿/硅叠层电池中,对电池进行QE和JV测试。电池的顶电池积分电流密度由15.42mA/cm2提升至15.60mA/cm2,底电池积分电流密度由13.86mA/cm2提升至14.36mA/cm2,叠层电池的器件效率由17.98%提升至18.63%;电池的QE积分电流密度和器件效率的提升幅度分别为0.50mA/cm2和3.49%。
实施例4:
以实施例2制得的绒度PDMS固化胶为衬底,采用旋涂法在衬底表面涂布一层厚度为0.5mm的紫外胶,转速500rpm,共30s;在紫外灯下照射5min后,将PDMS固化胶模板、固化后的薄膜和硅衬底撕开后分离;以固化后的薄膜为减反射膜,应用于CIGS/硅叠层电池中,对电池进行QE和JV测试,计算出叠层电池的QE积分电流密度和器件效率的提升幅度分别为1.06mA/cm2和6.63%。
实施例5:
在n型单晶硅衬底上以PS小球自组装、而后RIE刻蚀的方法,制备直径为2μm的柱状阵列结构;对衬底绒度结构表面进行RCA清洗;采用旋涂法,在衬底表面涂布一层厚度为0.05mm的紫外胶;在紫外灯下照射2min后,将固化后的薄膜和硅衬底撕开后分离;以固化后的薄膜为减反射膜,应用于a-Si/μc-Si叠层太阳电池中,对电池进行QE和JV测试,计算出叠层电池的QE积分电流密度和器件效率的提升幅度分别为1.08mA/cm2和8.69%。
实施例6:
在n型单晶硅衬底上以金属催化腐蚀的方法制备随机纳米结构绒度表面,尺寸20-100nm;采用旋涂法,在衬底表面涂布一层厚度为0.1mm的PDMS固化胶;放入真空腔室,抽真空至0.05kPa,静置0.5小时;而后在室温静置12小时,冲腔后取出;然后将固化胶与衬底分离,得到具有绒度结构的固化胶;将其做为减反射膜,应用于a-Si/nc-Si/nc-Si叠层太阳电池中,对电池进行QE和JV测试,计算出叠层电池的QE积分电流密度和器件效率的提升幅度分别为1.23mA/cm2和12.3%。
以上仅为本发明的较佳实施例,在具体实施方式及应用范围上均会有改变之处,本说明书内容不应理解为对本发明的限制。
Claims (10)
1.一种减反射膜的制备方法,其特征在于,包括步骤:
S1:在衬底上制备绒度结构;
S2:在绒度结构表面均匀涂布一层固化胶;
S3:对固化胶进行固化处理;
S4:将绒度结构衬底与固化胶分离,得到具有绒度结构的减反射膜。
2.如权利要求1所述的减反射膜的制备方法,其特征在于,所述步骤S1中的衬底为:硅片、玻璃、铝箔、铜箔、不锈钢板、PET、PEN或PDMS;所述绒度结构为周期性阵列结构或非周期性随机结构;所述绒度结构具体为:线状、柱状、碗状、金字塔状、花瓣状或羽翼状中的一种或两种以上的任意组合;所述绒度结构的微观尺寸为1nm-100μm,优选为1μm-10μm。
3.如权利要求1所述的减反射膜的制备方法,其特征在于,所述步骤S2中固化胶为:透明硅胶、透明灌封胶、透明水晶胶或紫外固化胶;所述涂布方法为:喷涂法、点胶机涂布法、旋涂法、刮涂法、狭缝涂布法、喷墨涂布法、倾倒涂布法、铸模涂布法、网版印刷法、胶版印刷法或凹版印刷法;所述减反射膜的厚度为0.05-5mm,优选为0.05-2mm;进一步优选为0.05-1mm。
4.如权利要求1所述的减反射膜的制备方法,其特征在于,所述固化胶由PDMS和固化剂以10:1体积比混合后组成。
5.如权利要求1所述的减反射膜的制备方法,其特征在于,所述步骤S2涂布固化胶之前还包括对绒度结构表面进行处理,所述表面处理为:去离子水清洗、盐酸溶液清洗、氢氟酸溶液清洗、RCA清洗、紫外光处理、可见光处理或氢等离子体处理中的一种或两种以上的任意组合,处理时间10秒-30分钟,优选为0.5-5分钟。
6.如权利要求1所述的减反射膜的制备方法,其特征在于,所述步骤S3进行固化处理之前还包括:抽真空静置5-60分钟,优选为静置10-30分钟,气压-100-100kPa,优选为0-10kPa。
7.如权利要求1所述的减反射膜的制备方法,其特征在于,所述步骤S3的处理条件为:采用热固化时,气压-100-100kPa,优选为0-10kPa;温度20-200℃,优选为50-120℃,进一步优选为70-100℃;时间1分钟-24小时,优选为0.5-15小时,进一步优选为1-8小时;或者,采用光源固化时,处理时间0.5分钟-24小时,优选为1分钟-6小时,进一步优选为1-60分钟,所述光源为:点光源、脉冲光源、紫外灯或高密度灯。
8.如权利要求1所述的减反射膜的制备方法,其特征在于,所述步骤S4之后,还包括对减反射膜进行表面处理,所述表面处理为:去离子水清洗、乙醇清洗、异丙醇清洗、乙二醇清洗、聚乙二醇清洗、盐酸溶液清洗、氢氟酸溶液清洗、RCA清洗、紫外光处理、可见光处理或氢等离子体处理中的一种或两种以上的任意组合,处理时间10秒-30分钟,优选为0.5-5分钟;其中的液体处理步骤优选在超声振荡及10-50℃条件下进行。
9.一种叠层太阳电池,其特征在于,所述叠层太阳电池包括由隧穿结连接的n个子电池,n为大于等于1的整数,其中:n个子电池中,顶电池受光面的透明电极上方包括如权利要求1至8任一项方法制备的减反射膜;优选减反射膜的绒面为受光面。
10.一种钙钛矿/硅叠层太阳电池,其特征在于,所述叠层太阳电池自下而上依次包括:(P1)硅异质结底电池:金属背电极/n型硅薄膜/本征钝化层/n型晶硅衬底/本征钝化层/p型硅薄膜;(P2)隧穿结:TCO或掺杂硅薄膜层;(P3)钙钛矿顶电池:ETL/钙钛矿/HTL;(P4)透明电极TCO,及正面金属电极;(P5)如权利要求1至8的任一项方法制备的减反射膜;优选减反射膜的绒面为受光面。
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