CN113436780A - 太阳能电池电极形成用组合物及由其形成的太阳能电池电极 - Google Patents
太阳能电池电极形成用组合物及由其形成的太阳能电池电极 Download PDFInfo
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Abstract
提供一种太阳能电池电极形成用组合物及由其形成的太阳能电池电极,所述太阳能电池电极形成用组合物包含导电粉,玻璃料,有机载体及少量化合物。
Description
技术领域
涉及一种太阳能电池电极形成用组合物及由其形成的太阳能电池电极,更具体地涉及一种印刷性优秀且线宽渗色较少的太阳能电池电极形成用组合物及由其形成的太阳能电池电极。
背景技术
随着化石燃料能源的枯竭,作为新的替代能源,利用太阳光的太阳能电池备受关注。太阳能电池构成为利用将太阳光的光子(photon)转化为电流的p-n结光伏效应(photovoltaic effect)来产生电能。在太阳能电池中,分别在具有p-n结的半导体晶片或衬底的上表面和下表面形成前电极和后电极,并被操作为由入射到晶片的太阳光诱发p-n结处的光伏效应,由此产生的电子经由电极向外部提供电流。这种太阳能电池的电极,可通过对电极用浆料进行涂布、图案化和烧成而形成在晶片表面上。
在这种太阳能电池中,提高将太阳能转化为电流的转换效率至关重要,而一直以来现有的太阳能电池电极形成用组合物主要通过导电粉的大小、表面处理方法或控制混合比例来提高太阳能电池转换效率。然而,仅以这样的方法来提高太阳能电池转换效率,则有局限性,而通过混合具有不同粒径的导电粉来改善烧结密度或电极电阻的尝试,也在印刷性和图案化上存在局限性。因此,需要开发一种浆料,其通过改善有机物来提高太阳能电池的转换效率,同时改善进行丝网印刷时的从网孔(mesh)的放电性,从而线宽窄,而线高增加,能够形成纵横比高的前电极。
发明内容
本发明的目的是提供一种印刷性优秀且线宽渗色较少的太阳能电池电极形成用组合物。
本发明的另一个目的是提供一种由所述组合物形成的太阳能电池电极。
1.根据一个方面,提供一种太阳能电池电极形成用组合物。所述组合物包含:导电粉;玻璃料;有机载体;以及由化学式1表示的化合物。
[化学式1]
在所述化学式1中;
R1至R9彼此独立地选自C1-C10烷基;
R10选自*-O-*’,*-NH-*’,C1-C10亚烷基及其组合;
R11选自氢和C1-C10烷基;
R12选自C1-C10烷基;
m和n彼此独立地选自1至20000的整数;
*和*’是与相邻原子的键合位点。
2.所述1中,R1至R9可以为甲基。
3.所述1或2中,*-R10-*'为*-(CH2)a-*'或*-(CH2)a1-NH-(CH2)a2-*';
a选自1至10的整数;
a1选自1至9的整数;
a2选自1至9的整数;
a1+a2可以为2至10。
4.在所述1至3中的任一项中,R11可以为氢。
5.在所述1至4中的任一项中,R12可选自C12-C25烷基。
6.在所述1至5中的任一项中,所述组合物可包含:
60重量%至95重量%的所述导电粉;
0.1重量%至20重量%的所述玻璃料;
1重量%至30重量%的所述有机载体;以及
0.01重量%至5重量%的由所述化学式1表示的化合物。
7.在所述1至6中的任一项中,所述组合物还可以包含分散剂、触变剂、塑化剂、粘度稳定剂、消泡剂、颜料、紫外线稳定剂、抗氧化剂及偶合剂中的一种以上。
8.根据另一个方面,提供一种太阳能电池电极。所述太阳能电池电极可由所述1至7中的任一组合物形成。
发明效果
本发明具有以下效果:提供一种印刷性优秀且线宽渗色较少的太阳能电池电极形成用组合物及由其形成的太阳能电池电极。
附图说明
图1是根据本发明的一个实施例的太阳能电池的示意图。
具体实施方式
在本文中,除非上下文中另有明确说明,所使用的单数形式旨在也包括复数形式。
在本文中,所使用的术语“包括(comprises/comprising)和/或包含(includes/including)”是指存在本文中描述的特征和/或构成要素,但并非排除添加一个以上的其他特征和/或构成要素。
在解释构成要素时,即使没有另外明确描述,也解释为包含误差范围。
在本文中,在表示数值范围的“a至b”中,将“至”定义为≥a且≤b。
在本文中,*和*'表示与相邻原子的键合位点。
太阳能电池电极形成用组合物
根据一个方面的太阳能电池电极形成用组合物可以包含导电粉、玻璃料、有机载体以及由化学式1表示的化合物。
下面,将详细说明太阳能电池电极形成用组合物的各个组分。
导电粉
导电粉可以包含但不限于,例如银(Ag)、金(Au)、铂(Pt)、钯(Pd)、铝(Al)以及镍(Ni)中的一个以上的金属粉。根据一个实施例,导电粉可以包含银粉。
导电粉的粒子形状没有特别限制,可以使用各种形状的粒子,例如球形、薄片形、非晶形等形状的粒子。
导电粉可以是具有纳米级或微米级粒径的粉末,例如数十纳米至数百纳米级的导电粉,或者可以是数微米至数十微米级的导电粉。另外,作为导电粉,也可以将具有两种以上不同尺寸的导电粉混合使用。
导电粉的平均粒径(D50)可以是0.1至10μm,例如可以是0.5至5μm。在所述范围内,接触电阻和串联电阻可能变低。在25℃下,在异丙醇(IPA)中对导电粉进行超声波分散三分钟后,利用CILAS公司制造的1064LD模型来测量所述平均粒径(D50)。
导电粉的使用量并没有特别限制,例如,导电粉的含量以太阳能电池电极形成用组合物的总重量计可以为60至95重量%(例如,70至90重量%)。在所述范围内,太阳能电池的转换效率优异,可以顺利进行糊化。
玻璃料
玻璃料为:在太阳能电池电极形成用组合物的烧成工艺中蚀刻(etching)抗反射膜,并熔融导电粉,以便在发射极区域形成导电粉的晶粒。另外,玻璃料改善导电粉和晶片之间的粘着性,并且在烧结时软化,从而诱发进一步降低烧成温度的效果。
玻璃料可包含选自以下元素中的一种或多种:铅(Pb)、碲(Te)、铋(Bi)、锂(Li)、磷(P)、锗(Ge)、镓(Ga)、铈(Ce)、铁(Fe)、硅(Si)、锌(Zn)、钨(W)、镁(Mg)、铯(Cs)、锶(Sr)、钼(Mo)、钛(Ti)、锡(Sn)、铟(In)、钒(V)、钡(Ba)、镍(Ni)、铜(Cu)、钠(Na)、钾(K)、砷(As)、钴(Co)、锆(Zr)、锰(Mn)以及铝(Al)。
例如,玻璃料可包含Bi-Te-O玻璃料、Pb-Bi-O玻璃料、Pb-Te-O玻璃料、Pb-Te-Bi-O玻璃料、Te-B-O玻璃料、Te-Ag-O玻璃料、Pb-Si-O玻璃料、Bi-Si-O玻璃料、Te-Zn-O玻璃料、Bi-Te-Li-Zn-玻璃料,Bi-B-O玻璃料,Pb-B-O玻璃料、Bi-Mo-O玻璃料、Mo-B-O玻璃料以及Te-Si-O玻璃料中的一个或多个。在这种情况下,可具有太阳能电池电极的电性质平衡优异的优点。
玻璃料的形状和大小等没有特别限制。例如,玻璃料的形状可以是球形或非晶形,玻璃料的平均粒径(D50)可以是0.1至10μm。在25℃下,将玻璃料超声波在异丙醇中分散三分钟后,使用CILAS公司制造的1064LD模型测量所述平均粒径(D50)。
玻璃料可使用常规方法由上述金属和/或金属氧化物来制备。例如,可以通过以下方法获得:使用球磨机(ball mill)或行星式球磨机(planetary mill)等混合上述金属和/或金属氧化物后,在800至1300℃中熔融混合后的组合物,在25℃下进行淬火(quenching),再通过盘磨机(disk mill)、行星式球磨机等粉碎所得产物。
玻璃料的使用量没有特别限制,例如,玻璃料的含量以太阳能电池电极形成用组合物的总重量计可以为0.1至20重量%(例如,0.1至10重量%)。在所述范围内,可在各种表面电阻下确保p-n结的稳定性,可使电阻最小化,最终可提高太阳能电池的效率。
有机载体
有机载体通过与太阳能电池电极形成用组合物的无机组分进行机械混合,而赋予组合物适于印刷的粘度及粘度流变学特性。
作为有机载体,通常可使用在太阳能电池电极形成用组合物中使用的有机载体,可包含粘合剂树脂和溶剂等。
作为粘合剂树脂可使用丙烯酸酯树脂或纤维素树脂等。例如,作为粘合剂树脂可使用乙基纤维素。举另一例来说,作为粘合剂树脂可使用:乙基羟乙基纤维素、硝化纤维素、乙基纤维素与酚树脂的混合物、醇酸树脂、酚醛树脂、丙烯酸酯树脂、二甲苯树脂、聚丁烯树脂、聚酯树脂、脲树脂、三聚氰胺树脂、乙酸乙烯酯树脂、木松香(rosin)或醇的聚甲基丙烯酸酯等。
作为溶剂,例如可以单独或混合使用己烷、甲苯、乙基溶纤剂(ethylCellosolve)、环己酮(cyclohexanone)、丁基溶纤剂(butyl Cellosolve)、丁基卡必醇(二乙二醇单丁醚)(butyl carbitol(diethylene glycol monobutyl ether))、二丁基卡必醇(二乙二醇二丁醚)(dibutyl carbitol(diethylene glycol dibutyl ether))、丁基卡必醇乙酸酯(二乙二醇单丁醚乙酸酯)(butyl carbitol acetate(diethylene glycolmonobutyl ether acetate))、丙二醇单甲醚(propylene glycol monomethyl ether)、己二醇(hexylene glycol)、松油醇(terpineol)、甲基乙基酮(methylethylketone)、苯甲醇(benzylalcohol)、γ-丁内酯(γ-butyrolactone)、乳酸乙酯(ethyl lactate)、2,2,4-三甲基-1,3-戊二醇单异丁酸酯(2,2,4-trimethyl-1,3-pentanediol monoisobutyrate)(例如,Texanol)。
有机载体的使用量并没有特别限制,例如,有机载体的含量以太阳能电池电极形成用组合物的总重量计可以为1至30重量%(例如,3至20重量%)。在所述范围内,可确保充分的粘接强度和优异的印刷性。
由化学式1表示的化合物
太阳能电池电极形成用组合物可包含由化学式1表示的化合物。
[化学式1]
由所述化学式1表示的化合物的摩擦系数及表面能比较低。因此,当由所述化学式1表示的化合物包含在太阳能电池电极形成用组合物中时,组合物放电容易,这有利于在进行丝网印刷时获得更多的印刷量,微细线宽放电容易,即使放电后也可以控制扩散。
在所述化学式1中,R1至R9可彼此独立地选自C1-C10烷基。例如,R1至R9可彼此独立地选自C1-C3烷基(例如,甲基,乙基,n-丙基和iso-丙基)。根据一个实施例,R1至R9可以是甲基,但不限于此。
在所述化学式1中,R10可选自*-O-*',*-NH-*',C1-C10亚烷基及其组合。例如,*-R10-*'为*-(CH2)a-*'或*-(CH2)a1-NH-(CH2)a2-*',其中a,a1和a2可分别为*-CH2-*'的数量,a可选自1至10(例如,2至4)的整数,a1可选自1至9(例如,2至4)的整数,a2可选自1至9(例如,1至3)的整数,a1+a2可以为2至10(例如,3至7),但不限于此。
在所述化学式1中,R11可选自氢及C1-C10烷基。例如,R11可选自氢及C1-C3烷基(例如,甲基、乙基、n-丙基及iso-丙基)。根据一个实施例,R11可以是氢,但不限于此。
在所述化学式1中,R12可选自C1-C60烷基。例如,R12可选自C10-C60烷基。根据一个实施例,R12可选自C10-C59烷基。根据另一个实施例,R12可选自C10-C25烷基。根据又一个实施例,R12可选自C12-C25烷基,但不限于此。
在所述化学式1中,m和n可彼此独立地选自1至20000的整数。其中,m可以是指*-O-Si(R1)(R5)-*'的数量,n可以是指*-O-Si(R6)(R10-N(R11)-CO-R12)-*'的数量。例如,m和n可彼此独立地选自1至10000的整数,再例如1至2000的整数,又例如10至2000的整数中,但不限于此。
由所述化学式1表示的化合物的使用量并没有特别限制,例如,所述化合物的含量以太阳能电池电极形成用组合物的总重量计可以为0.01重量%至5重量%。在所述范围内,有可能印刷性优异且线宽渗色较少。根据一个实施例,所述化合物的含量以太阳能电池电极形成用组合物的总重量计可以为0.1重量%至5重量%;根据另一个实施例,含量可以为0.3重量%至4重量%;根据又一个实施例,含量可以为0.5重量%至3重量%,但不限于此。
添加剂
为了提高流动特性、工艺特性和稳定性,除上述组分以外,太阳能电池电极形成用组合物根据需要还可以将以下添加剂单独含有或含有2种以上:分散剂、触变剂、塑化剂、粘度稳定剂、消泡剂、颜料、紫外线稳定剂、抗氧化剂,偶合剂等。这些的含量以太阳能电池电极形成用组合物的总重量计可以为0.1重量%至5重量%,但是根据需要可以变更其含量。
太阳能电池电极及包含该电极的太阳能电池
根据另一个方面,提供一种由所述太阳能电池电极形成用组合物形成的太阳能电池电极及包含太阳能电池电极的太阳能电池。图1是示出根据本发明的一个实施例的太阳能电池(100)的结构概略图。
参考图1,可通过以下方式来形成后电极(21)和前电极(23):将太阳能电池电极形成用组合物印刷在包含p层(或者n层)(11)及用作发射极的n层(或者p层)(12)的晶片或衬底(10)上,进行烧成。例如,可通过以下方式来执行制备后电极的初步工艺:将太阳能电池电极形成用组合物印刷涂布到晶片的背面,然后在200℃至400℃下,干燥10秒至60秒。此外,可通过将太阳能电池电极形成用组合物印刷在晶片的正面之后进行干燥来执行用于制备前电极的初步工艺。接着,可通过执行烧成工艺来形成前电极和后电极,所述烧成工艺是在400℃至950℃下,例如在600℃至950℃下烧成30秒至210秒。
以下,将参考实施例详细说明根据本发明一个实施例的太阳能电池电极形成用组合物。然而,这是作为本发明的优选实施例而提出的,在任何意义上都不能解释为对本发明的限制。
实施例
实施例1
在60℃下,对作为粘合剂树脂的乙基纤维素(STD4,Dow chemica公司)1.5重量份、作为溶剂的醇酯-12(texanol,Eastman公司)5.55重量份进行充分溶解后,添加作为导电粉的平均粒径(D50)为1.5μm的球形银粉(AG-5-11F,DowaHightech公司)89重量份,由氧化铋(15.8mol%)-氧化碲(53.8mol%)-氧化锌(13.2mol%)-氧化锂(17.2mol%)构成的、平均粒径(D50)为1.0μm且转化温度为273℃的Bi-Te-Zn-Li-O玻璃料2重量份,作为由化学式1表示的化合物的KF3935(Shinetsu公司)1.5重量份,以及多元羧酸分散剂(EFKA5054,BASF公司)0.45重量份,随后在三辊捏合机中混合及分散,从而制备太阳能电池电极形成用组合物。
实施例2至实施例4和比较例1
除了如下表1中所列改变每个组分的含量(单位:重量份)以外,以与所述实施例1相同的方式制备了太阳能电池电极形成用组合物。
【表1】
基于以下评估方法测量如上所述制备的实施例及比较例的太阳能电池电极形成用组合物的物理性质。测量结果表示在下表2。
评估例1:电性质的评估
在晶片(mono crystalline晶片为:对掺杂(doping)有硼(Boron)的p型晶片的正面进行纹理化(texturing),然后用POCl3形成n+层并在其上形成氮化硅(SiNx:H)的抗反射膜)的背面上印刷铝浆料之后,在300℃下干燥30秒。接着,使用28μm丝网掩模,将在实施例和比较例中制备的太阳能电池电极形成用组合物以一定的图案丝网印刷在晶片正面上,并且在300℃下干燥30秒。在940℃下,通过使用带式烧结炉将所述工艺形成的电池片(cell)烧成70秒来制备太阳能电池的电池片。针对这样制备的太阳能电池的电池片,使用太阳能电池的效率测量设备(Halm,Fortixtech公司)来测量转换效率(Eff.,单位:%),其结果如下表2所示。
评估例2:印刷性及线宽渗色评估
以以下方式获取电极:以一定图案将在实施例及比较例中制备的太阳能电池电极形成用组合物丝网印刷(丝网掩模:360目,乳液15,宽25μm)在结晶硅单晶片的正面上。电极的形状为梯形,所述电极是利用带式烧结炉,在375℃下干燥30秒至60秒,在600至900℃下烧成60秒至210秒而获得的,使用3D激光显微镜(VK-9700,KEYENCE公司)观察所述电极,并通过测量电极的厚度(单位:μm)及线宽(单位:μm)后,计算纵横比(厚度/线宽)来评估电极的扩散特性。此外,确认图案的短路状态,通过短路线路小于5个时标为○,5个以上时标为×来评估印刷性,其结果如下表2所示。
【表2】
从所述表2可以看出,包含本发明的由化学式1表示的化合物的实施例1至4的太阳能电池电极形成用组合物,与不包含的比较例1相比,同时满足线宽渗色特性和印刷性两者,还显示出由短路电流(Isc)的改善带来的效率改善的效果。
至此以实施例为中心对本发明进行了说明。本领域的技术人员可理解,在不脱离本发明的基本特征的情况下,可以以修改的形式来实现本发明。因此,所公开的实施例应从说明性的角度而非限制性的角度来考虑。本发明的范围不是由上述的说明而是由权利要求书所示,与其等同范围内的所有差异都应解释为包含在本发明中。
Claims (8)
2.根据权利要求1所述的太阳能电池电极形成用组合物,其中,
R1至R9为甲基。
3.根据权利要求1所述的太阳能电池电极形成用组合物,其中,
*-R10-*'为*-(CH2)a-*'或*-(CH2)a1-NH-(CH2)a2-*';
a选自1至10的整数;
a1选自1至9的整数;
a2选自1至9的整数;
a1+a2为2至10。
4.根据权利要求1所述的太阳能电池电极形成用组合物,其中,
R11为氢。
5.根据权利要求1所述的太阳能电池电极形成用组合物,其中,
R12选自C12-C25烷基。
6.根据权利要求1所述的太阳能电池电极形成用组合物,其中,包含:
60重量%至95重量%的所述导电粉;
0.1重量%至20重量%的所述玻璃料;
1重量%至30重量%的所述有机载体;以及
0.01重量%至5重量%的由所述化学式1表示的化合物。
7.根据权利要求1所述的太阳能电池电极形成用组合物,其中,
所述太阳能电池电极形成用组合物还包含分散剂、触变剂、塑化剂、粘度稳定剂、消泡剂、颜料、紫外线稳定剂、抗氧化剂及偶合剂中的中的一种以上。
8.一种太阳能电池电极,其由权利要求1至7中任一项所述的组合物形成。
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