CN103000251B - Solar cell silver-backed slurry with wide sintering process window - Google Patents
Solar cell silver-backed slurry with wide sintering process window Download PDFInfo
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- CN103000251B CN103000251B CN201210446522.5A CN201210446522A CN103000251B CN 103000251 B CN103000251 B CN 103000251B CN 201210446522 A CN201210446522 A CN 201210446522A CN 103000251 B CN103000251 B CN 103000251B
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- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 6
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Abstract
本发明涉及一种具有宽烧结工艺窗口的太阳能电池背银浆料。该背银浆料的组成及其重量百分数为：45-55%银粉、3-7%无铅无硅玻璃粉、10-15%有机粘合剂、20-40%溶剂、0.1-5%烧结促进剂、其他为助剂；其中，银粉由重量百分数为50-80%球形银粉和20-50%片状银粉组成。本发明背银浆料采用不同烧结活性的银粉搭配无铅无硅玻璃粉使用，并添加少量烧结促进剂，不同烧结活性的银粉可实现在较宽的烧结温度范围内形成致密的银膜结构，无铅无硅玻璃粉析晶度低，有利于促进银粉在宽烧结温度范围内在玻璃相中的溶解，并一定量烧结促进剂的添加可有效地避免银粉自凝聚形成块银，使得该背银浆料具有宽烧结工艺窗口。The invention relates to a solar battery back silver paste with a wide sintering process window. The composition and weight percentage of the back silver paste are: 45-55% silver powder, 3-7% lead-free silicon-free glass powder, 10-15% organic binder, 20-40% solvent, 0.1-5% sintering Accelerator and others are additives; wherein, the silver powder is composed of 50-80% spherical silver powder and 20-50% flake silver powder. The back silver paste of the present invention uses silver powders with different sintering activities together with lead-free and silicon-free glass powders, and adds a small amount of sintering accelerator. Silver powders with different sintering activities can form a dense silver film structure within a wide range of sintering temperatures. The lead-free and silicon-free glass powder has low devitrification, which is beneficial to promote the dissolution of silver powder in the glass phase in a wide range of sintering temperature, and the addition of a certain amount of sintering accelerator can effectively prevent the silver powder from agglomerating to form silver lumps, making the back silver The slurry has a wide sintering process window.
Description
技术领域 technical field
本发明涉及一种导电浆料，具体涉及一种具有宽烧结工艺窗口的的太阳能电池背银浆料。 The invention relates to a conductive paste, in particular to a solar battery back silver paste with a wide sintering process window.
背景技术 Background technique
太阳能电池是一种能将太阳能转化为电能的半导体器件。太阳能电池背银浆料是太阳能电池电子浆料的主要组成部分，它在太阳能电池生产中主要是用来制作背面主栅，起到将铝背场收集的电流汇流导出的作用。太阳能电池背面银浆主要由银粉、有机粘合剂、无机粘合剂、溶剂以及助剂组成。除了背银浆料的成本、导电性等性能指标外，烧结工艺窗口的宽窄也是考察背银浆料的一个关键指标，因为它影响着电池片生产的工艺质量以及最终成品太阳能电池片的良品率。因此，制备一种性能优异、具有宽烧结工艺窗口的背银浆料构成了太阳能电池生产中的一个关键技术要点。 A solar cell is a semiconductor device that converts solar energy into electricity. The solar cell back silver paste is the main component of the solar cell electronic paste. It is mainly used to make the back busbar in the production of solar cells, and plays the role of converging and exporting the current collected by the aluminum back field. The silver paste on the back of the solar cell is mainly composed of silver powder, organic binder, inorganic binder, solvent and additives. In addition to the cost, conductivity and other performance indicators of the back silver paste, the width of the sintering process window is also a key indicator for examining the back silver paste, because it affects the process quality of cell production and the yield of the final finished solar cell . Therefore, the preparation of a back silver paste with excellent performance and a wide sintering process window constitutes a key technical point in the production of solar cells.
目前，太阳能电池背银浆料使用单一形状的球状或片状银粉作为背银浆料的导电体。如申请号为201110200935.0的中国专利公开的一种使用单一的片状银粉为导电体的太阳能电池背银浆料，以及申请号为201110297031.4的中国专利公开的一种使用0.5-2 μm的球状银粉作为导电体的太阳能电池背银浆料，由于其所含的银粉烧结活性单一，这类背银浆料的烧结工艺窗口往往较窄。相比之下，太阳能电池正银浆料已逐渐采用球状或片状银粉的混合物作为银浆的导电体，如申请号为201110201638.8的中国专利公开的一种使用0.1-2 μm的粒状银粉和3-10 μm的片状银粉的混合物作为导电体的太阳能电池正银浆料，其中，球状和片状银粉具有不同的烧结活性，对应所得银浆具有较宽的烧结工艺窗口。但是目前这类正银浆料中采用的玻璃粉还是多为含硅玻璃粉，这类含硅玻璃粉热膨胀系数较低，但是析晶度高。这种析晶现象会使银浆的烧结工艺窗口变窄，即烧结工艺的参数变动易引起银粉在玻璃相中溶解的减少，进而导致块银的产生，使得含有不同烧结活性的银粉的银浆其宽烧结工艺窗口的特性无法体现。因此，制备一种性能优异、具有宽烧结工艺窗口的太阳能电池背银浆料，至少需要从银粉的烧结活性和玻璃粉的烧结工艺性能这两个角度进行综合考察。 At present, the back silver paste of solar cells uses single-shaped spherical or flake silver powder as the conductor of the back silver paste. For example, a Chinese patent with application number 201110200935.0 discloses a solar cell back silver paste that uses a single flake silver powder as a conductor, and a Chinese patent with application number 201110297031.4 discloses a spherical silver powder that uses 0.5-2 μm as The solar cell back silver paste of electrical conductor, because the silver powder contained in it has a single sintering activity, the sintering process window of this kind of back silver paste is often narrow. In contrast, the solar cell front silver paste has gradually adopted a mixture of spherical or flake silver powder as the conductor of the silver paste, such as a Chinese patent application number 201110201638.8 that uses 0.1-2 μm granular silver powder and 3 -A mixture of 10 μm flaky silver powder is used as a conductor for solar cell front silver paste. Among them, spherical and flaky silver powder have different sintering activities, and the corresponding silver paste has a wider sintering process window. However, at present, the glass powder used in this type of front-side silver paste is still mostly silicon-containing glass powder, which has a low coefficient of thermal expansion but a high degree of devitrification. This crystallization phenomenon will narrow the sintering process window of the silver paste, that is, the parameter change of the sintering process will easily lead to the reduction of the dissolution of the silver powder in the glass phase, which will lead to the generation of lump silver, making the silver paste containing silver powder with different sintering activity The characteristics of its wide sintering process window cannot be reflected. Therefore, the preparation of a solar cell back silver paste with excellent performance and a wide sintering process window requires at least a comprehensive investigation from the two perspectives of the sintering activity of the silver powder and the sintering process performance of the glass powder.
发明内容 Contents of the invention
本发明需要解决的技术问题在于克服现有技术的不足，提供一种性能优异、具有宽烧结工艺窗口的太阳能电池背银浆料。 The technical problem to be solved in the present invention is to overcome the deficiencies of the prior art, and provide a solar cell back silver paste with excellent performance and a wide sintering process window.
本发明需要解决的技术问题是通过以下技术方案实现的： The technical problem to be solved in the present invention is achieved through the following technical solutions:
一种具有宽烧结工艺窗口的太阳能电池背银浆料，其组成及其重量百分数为：银粉45-55%、无铅无硅玻璃粉3-7%、有机粘合剂10-15%、溶剂20-40%、烧结促进剂0.1-5%、余量为助剂，且各组分的重量百分数之和为100%。 A solar cell back silver paste with a wide sintering process window, its composition and weight percentages are: silver powder 45-55%, lead-free silicon-free glass powder 3-7%, organic binder 10-15%, solvent 20-40%, sintering accelerator 0.1-5%, and the rest are additives, and the sum of the weight percentages of each component is 100%.
上述银粉由重量百分数为50-80%球形银粉和20-50%片状银粉组成，球形银粉的振实密度>5g/cm3、平均粒径为0.2-1.5μm；片状银粉的振实密度>4.5g/cm3，平均厚度为0.1-0.2μm，平均横向尺寸为0.5-3μm。 The above-mentioned silver powder is composed of 50-80% by weight of spherical silver powder and 20-50% of flake silver powder. The tap density of the spherical silver powder is >5g/cm 3 and the average particle size is 0.2-1.5μm; >4.5g/cm 3 , the average thickness is 0.1-0.2μm, and the average lateral dimension is 0.5-3μm.
上述无铅无硅玻璃粉组成和重量百分数为：65-85%氧化铋、3-15%氧化硼、1-10%氧化锌、1-10%氧化铝、3-15%氧化钡、0.1-5%氧化钙、0.5-5%氧化钒和0-3%改性添加剂，其中改性添加剂为二氧化锆、五氧化二磷、二氧化钛和三氧化二钴中的一种，且玻璃粉各组分的重量百分数之和为100%。优选的技术方案为：无铅无硅玻璃粉组成和重量百分数为：72%氧化铋、8%氧化硼、5%氧化锌、5%氧化铝、4%氧化钡、3%氧化钙和3%氧化钒。 The composition and weight percentage of the above-mentioned lead-free and silicon-free glass powder are: 65-85% bismuth oxide, 3-15% boron oxide, 1-10% zinc oxide, 1-10% aluminum oxide, 3-15% barium oxide, 0.1- 5% calcium oxide, 0.5-5% vanadium oxide and 0-3% modifying additive, wherein the modifying additive is one of zirconium dioxide, phosphorus pentoxide, titanium dioxide and cobalt trioxide, and each group of glass powder The sum of weight percentages is 100%. The preferred technical scheme is: the composition and weight percentage of lead-free silicon-free glass powder are: 72% bismuth oxide, 8% boron oxide, 5% zinc oxide, 5% aluminum oxide, 4% barium oxide, 3% calcium oxide and 3% Vanadium oxide.
上述烧结促进剂为氧化银或碳酸银。 The above-mentioned sintering accelerator is silver oxide or silver carbonate.
上述有机粘合剂、溶剂和助剂为太阳能电池用电子浆料中通用的有机粘合剂、溶剂和助剂。 The above-mentioned organic binders, solvents and auxiliary agents are common organic adhesives, solvents and auxiliary agents in electronic pastes for solar cells.
与现有技术相比，本发明的优点和有益效果在于：本发明在配方上将不同烧结活性的银粉与无铅无硅玻璃粉搭配使用，并添加少量烧结促进剂；其中，不同烧结活性的银粉混合物作为背银浆料的导电体，可使银粉在较宽的烧结温度范围内形成致密的银膜结构，无铅无硅玻璃粉析晶度低，有利于促进银粉在宽的烧结温度范围内在玻璃相中的溶解，有效地避免银粉熔化凝聚形成块银，保证银层具有高的导电率；一定量的烧结促进剂可进一步避免银粉的自凝聚；通过不同烧结活性的银粉、无铅无硅玻璃粉以及少量烧结促进剂的搭配使用，使得该太阳能电池背银浆料具有宽烧结工艺窗口。 Compared with the prior art, the advantages and beneficial effects of the present invention are: in the present invention, silver powders with different sintering activities are used in combination with lead-free and silicon-free glass powders, and a small amount of sintering accelerator is added; among them, silver powders with different sintering activities The silver powder mixture is used as the conductor of the back silver paste, which can make the silver powder form a dense silver film structure in a wide range of sintering temperature. The dissolution in the inner glass phase effectively prevents the silver powder from melting and agglomerating to form a block of silver, ensuring that the silver layer has high conductivity; a certain amount of sintering accelerator can further avoid the self-coagulation of the silver powder; through different sintering activities of silver powder, lead-free and The combination of silica glass powder and a small amount of sintering accelerator makes the solar cell back silver paste have a wide sintering process window.
具体实施方式 Detailed ways
下面结合实施例，对本发明的具体实施方式做进一步描述。以下实施例仅用于更加清楚地说明本发明的技术方案，而不能以此来限制本发明的保护范围。 The specific implementation manner of the present invention will be further described below in conjunction with the examples. The following examples are only used to illustrate the technical solution of the present invention more clearly, but not to limit the protection scope of the present invention.
实施例1 Example 1
一种具有宽烧结工艺窗口的太阳能电池背银浆料，其组份及其重量百分数为：55%银粉、7%无铅无硅玻璃粉、10%丙烯酸树脂、20%松油醇、5%氧化银、3%为BYK-110。其中，银粉由重量百分数为80%球形银粉和20%片状银粉组成，球形银粉的振实密度>5g/cm3、平均粒径为0.2-1.5μm，片状银粉的振实密度>4.5g/cm3，平均厚度为0.1-0.2μm，平均横向尺寸为0.5-3μm；无铅无硅玻璃粉组成和重量百分数为：85%氧化铋、3%氧化硼、1%氧化锌、1%氧化铝、3%氧化钡、5%氧化钙、0.5%氧化钒和1.5%二氧化锆。 A solar cell back silver paste with a wide sintering process window, its components and weight percentages are: 55% silver powder, 7% lead-free silicon-free glass powder, 10% acrylic resin, 20% terpineol, 5% Silver oxide, 3% is BYK-110. Among them, the silver powder is composed of 80% spherical silver powder and 20% flake silver powder by weight percentage, the tap density of the spherical silver powder is >5g/cm 3 , the average particle size is 0.2-1.5μm, and the tap density of the flake silver powder is >4.5g /cm 3 , the average thickness is 0.1-0.2μm, and the average lateral dimension is 0.5-3μm; the composition and weight percentage of lead-free and silicon-free glass powder are: 85% bismuth oxide, 3% boron oxide, 1% zinc oxide, 1% oxide Aluminum, 3% barium oxide, 5% calcium oxide, 0.5% vanadium oxide and 1.5% zirconium dioxide.
实施例2 Example 2
一种具有宽烧结工艺窗口的太阳能电池背银浆料，其组份及其重量百分数为：45%银粉、3%无铅无硅玻璃粉、11%乙基纤维素、40%溶剂、0.1%碳酸银、0.9%BYK-110，其中，银粉由重量百分数为50%球形银粉和50%片状银粉组成，球形银粉的振实密度>5g/cm3、平均粒径为0.2-1.5μm，片状银粉的振实密度>4.5g/cm3，平均厚度为0.1-0.2μm，平均横向尺寸为0.5-3μm；无铅无硅玻璃粉组成和重量百分数为：65%氧化铋、15%氧化硼、4.9%氧化锌、2%氧化铝、5%氧化钡、0.1%氧化钙、5%氧化钒和3%五氧化二磷。 A solar cell back silver paste with a wide sintering process window, its components and weight percentages are: 45% silver powder, 3% lead-free silicon-free glass powder, 11% ethyl cellulose, 40% solvent, 0.1% Silver carbonate, 0.9% BYK-110, wherein the silver powder is composed of 50% spherical silver powder and 50% flake silver powder by weight, the tap density of the spherical silver powder is >5g/cm 3 , and the average particle size is 0.2-1.5μm. The tap density of silver powder is >4.5g/cm 3 , the average thickness is 0.1-0.2μm, and the average lateral dimension is 0.5-3μm; the composition and weight percentage of lead-free and silicon-free glass powder are: 65% bismuth oxide, 15% boron oxide , 4.9% zinc oxide, 2% aluminum oxide, 5% barium oxide, 0.1% calcium oxide, 5% vanadium oxide and 3% phosphorus pentoxide.
实施例3 Example 3
一种具有宽烧结工艺窗口的太阳能电池背银浆料，其组份及其重量百分数为：50%银粉、5%无铅无硅玻璃粉、10%甲基丙烯酸树脂、30%丁基卡比醇醋酸酯、3%氧化银、2%BYK-110；其中，银粉由重量百分数为70%球形银粉和30%片状银粉组成，球形银粉的振实密度>5g/cm3、平均粒径为0.2-1.5μm，片状银粉的振实密度>4.5g/cm3，平均厚度为0.1-0.2μm，平均横向尺寸为0.5-3μm；无铅无硅玻璃粉组成和重量百分数为：67%氧化铋、5%氧化硼、10%氧化锌、10%氧化铝、4%氧化钡、0.5%氧化钙、1.5%氧化钒和2%二氧化钛。 A solar cell back silver paste with a wide sintering process window, its components and their weight percentages are: 50% silver powder, 5% lead-free silicon-free glass powder, 10% methacrylic resin, 30% butyl carb Alcohol acetate, 3% silver oxide, 2% BYK-110; Among them, the silver powder is composed of 70% spherical silver powder and 30% flake silver powder, the tap density of the spherical silver powder is >5g/cm 3 , and the average particle size is 0.2-1.5μm, the tap density of flake silver powder is >4.5g/cm 3 , the average thickness is 0.1-0.2μm, and the average lateral dimension is 0.5-3μm; the composition and weight percentage of lead-free and silicon-free glass powder are: 67% oxidation Bismuth, 5% boron oxide, 10% zinc oxide, 10% aluminum oxide, 4% barium oxide, 0.5% calcium oxide, 1.5% vanadium oxide and 2% titanium dioxide.
实施例4 Example 4
一种具有宽烧结工艺窗口的太阳能电池背银浆料，其组份及其重量百分数为：54%银粉、6.5%无铅无硅玻璃粉、12%改性氢化蓖麻油、24%松节油、2.5%氧化银、1%BYK-110；其中，银粉由重量百分数为60%球形银粉和40%片状银粉组成，球形银粉的振实密度>5g/cm3、平均粒径为0.2-1.5μm，片状银粉的振实密度>4.5g/cm3，平均厚度为0.1-0.2μm，平均横向尺寸为0.5-3μm；无铅无硅玻璃粉组成和重量百分数为：70%氧化铋、8%氧化硼、8%氧化锌、2%氧化铝、3%氧化钡、3%氧化钙、4%氧化钒和2%三氧化二钴。 A solar cell back silver paste with a wide sintering process window, its components and percentages by weight are: 54% silver powder, 6.5% lead-free silicon-free glass powder, 12% modified hydrogenated castor oil, 24% turpentine, 2.5% % silver oxide, 1% BYK-110; among them, the silver powder is composed of 60% spherical silver powder and 40% flake silver powder by weight, the tap density of the spherical silver powder is >5g/cm 3 , and the average particle size is 0.2-1.5μm. The tap density of flake silver powder is >4.5g/cm 3 , the average thickness is 0.1-0.2μm, and the average lateral dimension is 0.5-3μm; the composition and weight percentage of lead-free and silicon-free glass powder are: 70% bismuth oxide, 8% oxide Boron, 8% zinc oxide, 2% aluminum oxide, 3% barium oxide, 3% calcium oxide, 4% vanadium oxide and 2% cobalt trioxide.
实施例5 Example 5
一种具有宽烧结工艺窗口的太阳能电池背银浆料，其组份及其重量百分数为：52%银粉、6%无铅无硅玻璃粉、13%丙烯酸树脂、27%松油醇、1%碳酸银、1%BYK-110；其中，银粉由重量百分数为55%球形银粉和45%片状银粉组成，球形银粉的振实密度>5g/cm3、平均粒径为0.2-1.5μm，片状银粉的振实密度>4.5g/cm3，平均厚度为0.1-0.2μm，平均横向尺寸为0.5-3μm；无铅无硅玻璃粉组成和重量百分数为：72%氧化铋、8%氧化硼、5%氧化锌、5%氧化铝、4%氧化钡、3%氧化钙和3%氧化钒。 A solar cell back silver paste with a wide sintering process window, its components and weight percentages are: 52% silver powder, 6% lead-free silicon-free glass powder, 13% acrylic resin, 27% terpineol, 1% Silver carbonate, 1% BYK-110; Among them, the silver powder is composed of 55% spherical silver powder and 45% flake silver powder, the tap density of the spherical silver powder is >5g/cm 3 , and the average particle size is 0.2-1.5μm. The tap density of silver powder is >4.5g/cm 3 , the average thickness is 0.1-0.2μm, and the average lateral dimension is 0.5-3μm; the composition and weight percentage of lead-free and silicon-free glass powder are: 72% bismuth oxide, 8% boron oxide , 5% zinc oxide, 5% aluminum oxide, 4% barium oxide, 3% calcium oxide and 3% vanadium oxide.
上述各实施方案是对本发明的上述内容作出的进一步说明，但不应理解为本发明上述主题的范围仅限于上述实施例。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。 The above embodiments are further descriptions of the above contents of the present invention, but it should not be understood that the scope of the above subject matter of the present invention is limited to the above examples. It should be pointed out that those skilled in the art can make some improvements and modifications without departing from the technical principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.
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| EP2896602B1 (en) * | 2014-01-16 | 2017-08-09 | Heraeus Precious Metals North America Conshohocken LLC | Low-silver electroconductive paste |
| CN104778988B (en) * | 2014-01-09 | 2017-10-24 | 上海贺利氏工业技术材料有限公司 | Low conductive silver slurry |
| US20150194546A1 (en) * | 2014-01-09 | 2015-07-09 | Heraeus Precious Metals North America Conshohocken Llc | Low-silver electroconductive paste |
| CN104465875B (en) * | 2014-12-05 | 2016-09-21 | 清华大学 | A kind of preparation method of photovoltaic cell silver grid wire |
| JP2016213284A (en) * | 2015-05-01 | 2016-12-15 | 東洋アルミニウム株式会社 | Aluminum paste composition for PERC type solar cell |
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| CN105185429B (en) * | 2015-08-07 | 2019-01-18 | 昆明贵信凯科技有限公司 | Base metal electric slurry encasement medium slurry and its application |
| CN107068240A (en) * | 2017-02-20 | 2017-08-18 | 江苏瑞德新能源科技有限公司 | A kind of back silver paste |
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