CN108538447A - 硅粉改性晶体硅太阳能电池复合银电极浆料及制备方法 - Google Patents
硅粉改性晶体硅太阳能电池复合银电极浆料及制备方法 Download PDFInfo
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- CN108538447A CN108538447A CN201810553380.XA CN201810553380A CN108538447A CN 108538447 A CN108538447 A CN 108538447A CN 201810553380 A CN201810553380 A CN 201810553380A CN 108538447 A CN108538447 A CN 108538447A
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- silver
- powder
- silica flour
- solar cell
- oxide
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 150
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 235000013312 flour Nutrition 0.000 title claims abstract description 75
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 75
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 50
- 239000004332 silver Substances 0.000 title claims abstract description 50
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 23
- 239000010703 silicon Substances 0.000 title claims abstract description 23
- 239000013078 crystal Substances 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002003 electrode paste Substances 0.000 title claims description 16
- 239000000843 powder Substances 0.000 claims abstract description 60
- 239000011521 glass Substances 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000007873 sieving Methods 0.000 claims abstract description 18
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 238000010791 quenching Methods 0.000 claims abstract description 10
- 230000000171 quenching effect Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 7
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- 238000001514 detection method Methods 0.000 claims abstract description 3
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
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- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 11
- -1 NC Nitroncellulose Polymers 0.000 claims description 10
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- 238000002156 mixing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 7
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- 238000001291 vacuum drying Methods 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
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- 239000010959 steel Substances 0.000 claims description 5
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
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- 230000006698 induction Effects 0.000 claims description 4
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- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical group CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940116411 terpineol Drugs 0.000 claims description 3
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
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- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 claims description 2
- 239000001293 FEMA 3089 Substances 0.000 claims description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims 1
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- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- UYKQQBUWKSHMIM-UHFFFAOYSA-N silver tungsten Chemical compound [Ag][W][W] UYKQQBUWKSHMIM-UHFFFAOYSA-N 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910001097 yellow gold Inorganic materials 0.000 description 1
- 239000010930 yellow gold Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
本发明公开了硅粉改性晶体硅太阳能电池复合银电极浆料及其制备方法,包括如下步骤:1)制备玻璃粉:称取原料,混合均匀,进行熔炼,然后取出,水淬、粉碎、球磨、过筛,干燥后过筛得到玻璃粉;2)制备有机载体:称取树脂和有机溶剂,将树脂溶于有机溶剂中,再加入分散剂和防沉剂作为助剂,搅拌均匀形成有机载体;3)称取银粉、银包硅粉、玻璃粉、金属氧化物粉添加到有机载体中,搅拌均匀,研磨,真空脱气,检测合格即得本发明电极浆料。
Description
技术领域
本发明属于电子材料,涉及电子、化工和材料领域,涉及一种太阳能电池正面电极银浆及制备方法,具体涉及硅粉改性晶体硅太阳能电池复合银电极浆料及制备方法。
背景技术
晶体硅太阳能电池是目前市场占有率最高的太阳能电池,因其使用寿命长,持续使用时间可超过50年。金属化电极是晶体硅太阳能电池的关键材料,尤其是正面栅极材料,直接影响太阳能电池的光电转化效率、填充影子、串联电阻等性能指数,所以,正面电极银浆的质量和性能的好坏直接决定着电池的使用寿命和衰减度。正面银浆通过丝网印刷工艺实现金属化,为尽可能减少遮光面,同时要腐蚀透SiNx减反射膜,形成较理想的Ag-Si欧姆接触,实现p-n结电流的有效导出,但是SiNx层到p-n结的距离只有0.35μm左右,在腐蚀SiNx层时,很难在工业生产中实现一致且理想的腐蚀深度,因此,在电极烧结时,与电极接触的SiNx层完全腐蚀和p-n结的结构不被破坏是电极材料实现高效、稳定、长寿命的关键。
正面电极银浆主要由导电粉末、无机粘结材料、有机载体和添加剂组成,导电粉末在烧结后形成导电线路,并实现电池与外接焊带之间的电流导通;无机粘结材料在烧结过程中烧穿SiNx减反射膜,实现银电极与硅之间的联通和粘结;有机载体使电极浆料有良好的印刷性能,实现理想的印刷要求。
作为晶体硅太阳能电池的关键材料,在如何提高材料性能方面,已有较多的研究成果,专利CN104157331A,CN103000250A,CN102426872A和CN106128550A中,通过掺入银包铜作为导电相代替部分银粉,专利CN106876000A中,浆料中的金属粉选择核材料为:钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、铍、钨、镁、钇、锆、铌、钼、锝、镉等氢化物中的一种或几种,壳材料为:金属银。专利CN103650238A,CN103596648A,CN103545016A,CN103545015A中的金属粉用银、金、铂、铜、铁、镍、锌、钛、钴、铬、铝、锰、钯、铑中的至少一种或者银包覆的铜、铁、镍、锌、钛、钴、铬、铝、锰的至少一种。专利CN105810284A中,银粉中添加铜粉、银包铝合金粉、磷酸铁锂/碳纳米管复合材料作为导电相;专利CN106297954A中,使用片状锌粉、球状铜粉、银包铝合金粉、磷酸铁锂/碳纳米管复合材料作为导电相;专利CN105655416A,CN105810286A,CN105810287A,CN105655007A及CN105655010A中使用银粉、锌粉、银包镍合金粉、磷酸铁锂/碳纳米管复合材料作为导电相;专利CN106782755A中用纯银粉、纯镍粉、镍包石墨粉、银包铝粉、银包铜粉、银包镍粉、银包玻璃粉中的任意一种或两种及以上的混合物。专利CN103106952A中用银粉、锡粉、银包镍粉、银包铜粉组成导电相。专利CN102426873A中添加银磷铜合金作为导电相,专利CN102610297A添加银包铜作为导电相,专利CN103700428A用包覆有镍镀层或锡镀层、银镀层的铜粉取代部分银粉作为导电相,专利CN1070682441A中在导电金属粉中加入镉银合金粉、银锡合金粉、银碳合金、银镍合金、银镁合金、银铜锌合金、银铜合金、银钼合金、银钨合金、银铁合金、银铜锡锌合金、银锰合金,专利CN104575666A通过纳米银包覆高分子微球颗粒作为导电相降低成本。
但在取代部分银导电相的同时,如何能使浆料保持用纯银粉作为导电相时所具有焊接性能好、导电率高、难氧化的优点。因此,在降低成本的同时,如何保证浆料在使用性能上得到保持或提高,是需要努力的方向。
但上述专利中通过添加其他金属粉,或者添加的银包贱金属粉会存在包覆不完全或包覆层不均匀的现象,在未添加其他保护剂的情况下,在烧结过程容易发生氧化,导致粉的导电率下降,造成电极整体性能降低。添加的合金粉虽然抗氧化得到了提高,但电导率没有纯银的理想,会造成电池的光电转换效率降低。
本发明在中国专利申请201711205976.2基础上,先在硅粉表面利用化学沉积得到银包硅粉,然后对该银包硅粉及添加的银粉进行有机包覆处理,既能提高硅粉的抗氧化能力,保证电极浆料电导率的稳定性,也能使得银包覆后的硅粉与纯银粉保持同样的电性能,且电池的短路电流减小,光电转换效率明显提高,电极浆料印刷性更好。
发明内容
本发明目的在于提供硅粉改性晶体硅太阳能电池复合银电极浆料及制备方法,用于替代目前纯金属粉作为导电相的高银含量浆料,并提高印刷性能和使用效果。
本发明所述的硅粉改性晶体硅太阳能电池复合银电极浆料,由以下组分制成:
银粉5.0-50.0wt%、银包硅粉40.0-85.0wt%、玻璃粉2.0-8.0wt%、0-3.0wt%金属氧化物粉、有机载体6.0-30.0wt%;
所述的银粉,粒径为0.5-1.6μm、振实密度为3.2-6.0g/cm3的类球形银粉;
所述的银包硅粉,银含量为25.0-35.0%的粉体、粒径为0.1-0.6μm、振实密度为0.2-1.2g/cm3;
所述银包硅粉中的硅粉采用射频感应等离子体制备技术制备;
所述的银粉和银包硅粉都经过有机包覆处理,过程是:按照银粉和银包硅粉总重量的0.05%、0.2%和0.05%分别称取乙基纤维素、丁基卡必醇和十二胺,加入到银粉和银包硅粉总重量50%的无水乙醇中,用高速分散机以600转/分的转速连续搅拌6小时,制取有机包覆液体,再将银粉和银包硅粉倒入上述包覆液体中,用高速分散机以1200转/分的转速连续搅拌30分钟,在真空烘箱中60℃烘干4小时,200目过筛。
本发明还涉及上述的硅粉改性晶体硅太阳能电池复合银电极浆料的制备方法,包括如下步骤:
1)制备玻璃粉:称取原料,混合均匀,进行熔炼,然后取出,水淬、粉碎、球磨、过筛,干燥后过筛得到玻璃粉;
2)制备有机载体:称取树脂和有机溶剂,将树脂溶于有机溶剂中,再加入分散剂和防沉剂作为助剂,搅拌均匀形成有机载体;
3)称取银粉、银包硅粉、玻璃粉、金属氧化物粉添加到有机载体中,搅拌均匀,研磨,真空脱气,检测合格即得本发明电极浆料;
所述的银粉和银包硅粉都经过有机包覆处理,过程是:按照银粉和银包硅粉总重量的0.05%、0.2%和0.05%分别称取乙基纤维素、丁基卡必醇和十二胺,加入到银粉和银包硅粉总重量50%的无水乙醇中,用高速分散机以600转/分的转速连续搅拌6小时,制取有机包覆液体,再将银粉和银包硅粉倒入上述包覆液体中,用高速分散机以1200转/分的转速连续搅拌30分钟,在真空烘箱中60℃烘干4小时,200目过筛。
本发明步骤1)所述的称取原料,称取1.0-8.0wt%氧化铋、18.0-70.0wt%氧化碲、15.0-65.0wt%氧化铅、1.0-3.0wt%氧化钠、2-8.0wt%五氧化二磷,1.0-12.0wt%氧化银,0-3.0wt%氧化硼中的几种。
步骤1)所述的混合均匀,进行熔炼,然后取出,水淬、粉碎、球磨、过筛,干燥后过筛得到玻璃粉,用三维混料机将上述原料混合均匀后,装于铂金坩埚,置于高温电阻炉中进行熔炼,于900-1100℃熔炼1小时,取出后水淬、粉碎、球磨、过筛,于65-75℃干燥后过筛得到玻璃粉,D100≤1.8μm。
步骤2)所述的树脂,为乙基纤维素、硝基纤维素、乙基羟乙基纤维素、木松香中的一种或多种,当混合时为任意比例;
所述的有机溶剂,为萜品醇、松节油、二乙二醇丁醚、二乙二醇二丁醚、丁基卡必醇醋酸酯、二丙二醇单甲醚、三丙二醇单甲醚中的一种或多种,当混合时为任意比例;
所述的分散剂,为表面活性剂司班85;
所述的防沉剂,为有机膨润土。
步骤2)所述的称取,按照4.0-15.0wt%树脂、78.0-88.0wt%有机溶剂、4.0-8.0wt%分散剂、2.0-6.0wt%防沉剂;
步骤2)所述的将树脂溶于有机溶剂中,再加入分散剂和防沉剂作为助剂,搅拌均匀形成有机载体,将有机溶剂加入不锈钢容器中混合,再在搅拌过程中加入树脂,升温至70-90℃,待树脂完全溶解完后,降温至40-50℃下加入表面活性剂和防沉剂,过滤得到透明的具有良好印刷性的有机载体。
步骤3)所述的称取银粉、银包硅粉、玻璃粉、金属氧化物粉添加到有机载体中,称取5.0-40.0wt%银粉、50.0-85.0wt%银包硅粉、2.0-4.0wt%玻璃粉、0-1.6wt%金属氧化物粉,添加到6.0-18.0wt%有机载体中;
步骤3)所述的银粉,粒径为0.5-1.6μm、振实密度为3.2-6.0g/cm3的类球形银粉;
所述的银包硅粉,银含量为25.0-35.0%的粉体、粒径为0.1-0.6μm、振实密度为0.2-1.2g/cm3;所述银包硅粉中的硅粉采用射频感应等离子体制备技术制备;
所述的金属氧化物粉,为氧化锌,氧化铋,氧化硼,氧化镁,氧化钠,氧化镍,氧化铜,氧化锆,氧化铈,氧化镨,氧化钒,五氧化二磷,氧化镧,氧化钛,氧化钴的一种或几种混合,当混合时为任意比例。
步骤3)所述的搅拌均匀,研磨,真空脱气,用高速分散机搅拌均匀,使用三辊研磨机研磨3-4遍,使用细度测试仪测试细度小于5μm为止,再用搅拌脱泡机真空脱气。
与现有技术相比,本发明具有以下优点:
1、本发明得到的银浆性能优良,烧结温度窗口宽:710-920℃/1-3s,丝网印刷质量优:400目不锈钢丝网印刷,线宽≤22m;可焊性优;
2、本发明因通过添加银包硅粉作为金属导电项,在低温烧结由于银的保护而不被氧化,在较高温度时,电极材料因烧结而结构变化,银包硅粉粒度较小,有效填充银颗粒的间隙,在烧结时的收缩率低,材料的致密性高,使得电极材料以及电极材与电池之间的接触电阻得到大大降低,光电转换效率高:单晶硅片≥22.0%,多晶硅片≥21.0%(太阳能模拟器在标准条件下测试);
3、易加工,使用三辊研磨机研磨3-4遍细度就小于5μm。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,下面对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1:
步骤A:制备玻璃粉:称取1.0wt%氧化铋,22.0wt%氧化碲,65.0wt%氧化铅,3.0wt%氧化钠,8.0wt%五氧化二磷,1.0wt%氧化银;用三维混料机将上述原料混合均匀后,装于铂金坩埚,置于高温电阻炉中进行熔炼,于1000℃熔炼1小时,取出后水淬、粉碎、球磨、过筛,于65℃干燥后过筛得到玻璃粉,平均粒径为0.2-0.8μm;
步骤B:制备有机载体:称取63.0wt%二乙二醇丁醚,12.0wt%二乙二醇二丁醚、12.0wt%丁基卡必醇醋酸酯,15.0wt%乙基纤维素,5.0wt%的表面活性剂司班85,2.0wt%的防沉剂有机膨润土;先将二乙二醇丁醚、二乙二醇二丁醚和丁基卡必醇醋酸酯加入不锈钢容器中混合,再在搅拌过程中加入乙基纤维素,升温至70-90℃,待树脂完全溶解完后,降温至40-50℃下加入表面活性剂司班85和有机膨润土,过滤得到透明的具有良好印刷性的有机载体;
步骤C:选用导电银粉和银包硅粉:特选形状包含平均粒径为1.6μm的类球形银粉,其振实密度6.0g/cm3;平均粒径为0.1μm的银包硅粉,振实密度为0.2g/cm3;以上导电粉体按照重量比4:5通过机械混合均匀,可以在浆料烧结过程中相互填充、交联,达到良好可焊性的目标;选用的银粉和银包硅粉都经过有机包覆处理,过程是:按照银粉和银包硅粉总重量的0.05%、0.2%和0.05%分别称取乙基纤维素、丁基卡必醇和十二胺,加入到银粉和银包硅粉总重量50%的无水乙醇中,用高速分散机以600转/分的转速连续搅拌6小时,制取有机包覆液体,再将银粉和银包硅粉倒入上述包覆液体中,用高速分散机以1200转/分的转速连续搅拌30分钟,在真空烘箱中60℃烘干4小时,200目过筛;
步骤D:制备电极浆料:按质量百分比40.0%的导电银粉,50.0%的银包硅粉,0.5%的金属氧化物粉(金属氧化物为氧化锌,氧化铋,氧化硼,氧化镁,氧化钠,氧化镍,氧化铜,氧化锆,氧化铈,氧化镨,氧化钒,五氧化二磷,氧化镧,氧化钛,氧化钴的一种或几种混合,混合时为任意比例),3.5%的玻璃粉,6.0%的有机载体配料并混合,用真空搅拌机搅拌均匀,调成糊状,用三辊研磨机研磨至细度≤5μm,即得到合格的电极银浆。
所制得正面电极浆料的性能:
浆料细度:≤5μm(研磨3遍);
丝网印刷:400目不锈钢丝网印刷,线宽≤22μm;
烧结温度:710-920℃/1-3s;
转换效率:单晶硅片≥22.0%,多晶硅片≥21.0%;
收缩率:≤6.5%。
实施例2:
步骤A:称取8.0wt%氧化铋,18.0wt%氧化碲,53.0wt%氧化铅,1.0wt%氧化钠,5.0wt%五氧化二磷,12.0wt%氧化银,3.0wt%氧化硼;用三维混料机将上述原料混合均匀后,装于铂金坩埚,置于高温电阻炉中进行熔炼,于1100℃熔炼1小时,取出后水淬、粉碎、球磨、过筛,于75℃干燥后过筛得到玻璃粉,平均粒径为0.3-1.5μm;
步骤B:制备有机载体:称取64.0wt%二乙二醇丁醚,15.5wt%二乙二醇二丁醚、10.0wt%丁基卡必醇醋酸酯,6.0wt%乙基纤维素,8.0wt%的表面活性剂司班85,6.0wt%的防沉剂有机膨润土。先将二乙二醇丁醚、二乙二醇二丁醚和丁基卡必醇醋酸酯加入不锈钢容器中混合,再在搅拌过程中加入乙基纤维素,升温至70-100℃,待树脂完全溶解完后,降温至40-50℃下加入表面活性剂司班85和有机膨润土,过滤得到透明的具有良好印刷性的有机载体;
步骤C:选用导电银粉和银包硅粉:特选形状包含平均粒径为0.5μm的类球形银粉,其振实密度3.2g/cm3;平均粒径为0.6μm的银包硅粉,振实密度为1.2g/cm3;以上导电粉体按照重量比5:85通过机械混合均匀,可以在浆料烧结过程中相互填充、交联,达到良好可焊性的目标;选用的银粉和银包硅粉都经过有机包覆处理,过程是:按照银粉和银包硅粉总重量的0.05%、0.2%和0.05%分别称取乙基纤维素、丁基卡必醇和十二胺,加入到银粉和银包硅粉总重量50%的无水乙醇中,用高速分散机以600转/分的转速连续搅拌6小时,制取有机包覆液体,再将银粉和银包硅粉倒入上述包覆液体中,用高速分散机以1200转/分的转速连续搅拌30分钟,在真空烘箱中60℃烘干4小时,200目过筛;
步骤D:制备电极浆料:按质量百分比5.0%的导电银粉,85.0%的银包硅粉,2.0%的玻璃粉,8.0%的有机载体配料并混合,用真空搅拌机搅拌均匀,调成糊状,用三辊研磨机研磨至细度≤5μm,即得到合格的电极银浆。
所制得正面电极浆料的性能:
浆料细度:≤5μm(研磨3遍);
丝网印刷:400目不锈钢丝网印刷,线宽≤22μm;
烧结温度:710-920℃/1-3s;
转换效率:单晶硅片≥22.0%,多晶硅片≥21.0%;
收缩率:≤6.2%。
实施例3:
步骤A:称取5.0wt%氧化铋,70.0wt%氧化碲,15.0wt%氧化铅,2.0wt%氧化钠,2.0wt%五氧化二磷,5.0wt%氧化银,1.0wt%氧化硼;用三维混料机将上述原料混合均匀后,装于铂金坩埚,置于高温电阻炉中进行熔炼,于900℃熔炼1小时,取出后水淬、粉碎、球磨、过筛,于70℃干燥后过筛得到玻璃粉,平均粒径为0.3-1.5μm;
步骤B:制备有机载体:称取60.0wt%二乙二醇丁醚,8.0wt%萜品醇,12.0wt%二乙二醇二丁醚、10.0wt%丁基卡必醇醋酸酯,3.0wt%乙基纤维素、1.0wt%硝基纤维素,4.0wt%的表面活性剂司班85,4.0wt%的防沉剂有机膨润土。先将二乙二醇丁醚、萜品醇、二乙二醇二丁醚和丁基卡必醇醋酸酯加入不锈钢容器中混合,再在搅拌过程中加入乙基纤维素,升温至70-90℃,待树脂完全溶解完后,降温至40-50℃下加入表面活性剂司班85和有机膨润土,过滤得到透明的具有良好印刷性的有机载体;
步骤C:选用导电银粉和银包硅粉。特选形状包含平均粒径为1.2μm的类球形银粉,其振实密度4.5g/cm3;平均粒径为0.5μm的银包硅粉,振实密度为1.0g/cm3;以上导电粉体按照重量比177:25通过机械混合均匀,可以在浆料烧结过程中相互填充、交联,达到良好可焊性的目标;选用的银粉和银包硅粉都经过有机包覆处理,过程是:按照银粉和银包硅粉总重量的0.05%、0.2%和0.05%分别称取乙基纤维素、丁基卡必醇和十二胺,加入到银粉和银包硅粉总重量50%的无水乙醇中,用高速分散机以600转/分的转速连续搅拌6小时,制取有机包覆液体,再将银粉和银包硅粉倒入上述包覆液体中,用高速分散机以1200转/分的转速连续搅拌30分钟,在真空烘箱中60℃烘干4小时,200目过筛;
步骤D:制备电极浆料:按质量百分比66%的导电银粉,10.0%的银包硅粉,2.0%的金属氧化物粉(金属氧化物为氧化锌,氧化铋,氧化硼,氧化镁,氧化钠,氧化镍,氧化铜,氧化锆,氧化铈,氧化镨,氧化钒,五氧化二磷,氧化镧,氧化钛,氧化钴的一种和几种混合,混合时为任意比例),4.0%的玻璃粉,18.0%的有机载体配料并混合,用真空搅拌机搅拌均匀,调成糊状,用三辊研磨机研磨至细度≤5μm,即得到合格的电极银浆。
所制得正面电极浆料的性能:
浆料细度:≤5μm(研磨3遍);
丝网印刷:400目不锈钢丝网印刷,线宽≤22μm;
烧结温度:710-920℃/1-3s;
转换效率:单晶硅片≥22.0%,多晶硅片≥21.0%;
收缩率:≤6.5%。
当然,本发明还可有其它多种实施例,在不背离本发明精神及其实质的情况下,熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形,但这些相应的改变和变形都应属于本发明的保护范围。
Claims (10)
1.硅粉改性晶体硅太阳能电池复合银电极浆料,其特征在于,由以下组分制成:
银粉5.0-50.0wt%、银包硅粉40.0-85.0wt%、玻璃粉2.0-8.0wt%、0-3.0wt%金属氧化物粉、有机载体6.0-30.0wt%;
所述的银粉,粒径为0.5-1.6μm、振实密度为3.2-6.0g/cm3的类球形银粉;
所述的银包硅粉,银含量为25.0-35.0%的粉体、粒径为0.1-0.6μm、振实密度为0.2-1.2g/cm3;
所述银包硅粉中的硅粉采用射频感应等离子体制备技术制备;
所述的银粉和银包硅粉都经过有机包覆处理,过程是:按照银粉和银包硅粉总重量的0.05%、0.2%和0.05%分别称取乙基纤维素、丁基卡必醇和十二胺,加入到银粉和银包硅粉总重量50%的无水乙醇中,用高速分散机以600转/分的转速连续搅拌6小时,制取有机包覆液体,再将银粉和银包硅粉倒入上述包覆液体中,用高速分散机以1200转/分的转速连续搅拌30分钟,在真空烘箱中60℃烘干4小时,200目过筛。
2.权利要求1所述的硅粉改性晶体硅太阳能电池复合银电极浆料的制备方法,其特征在于,包括如下步骤:
1)制备玻璃粉:称取原料,混合均匀,进行熔炼,然后取出,水淬、粉碎、球磨、过筛,干燥后过筛得到玻璃粉;
2)制备有机载体:称取树脂和有机溶剂,将树脂溶于有机溶剂中,再加入分散剂和防沉剂作为助剂,搅拌均匀形成有机载体;
3)称取银粉、银包硅粉、玻璃粉、金属氧化物粉添加到有机载体中,搅拌均匀,研磨,真空脱气,检测合格即得本发明电极浆料;
所述的银粉和银包硅粉都经过有机包覆处理,过程是:按照银粉和银包硅粉总重量的0.05%、0.2%和0.05%分别称取乙基纤维素、丁基卡必醇和十二胺,加入到银粉和银包硅粉总重量50%的无水乙醇中,用高速分散机以600转/分的转速连续搅拌6小时,制取有机包覆液体,再将银粉和银包硅粉倒入上述包覆液体中,用高速分散机以1200转/分的转速连续搅拌30分钟,在真空烘箱中60℃烘干4小时,200目过筛。
3.根据权利要求2所述的硅粉改性晶体硅太阳能电池复合银电极浆料的制备方法,其特征在于:步骤1)所述的称取原料,是称取质量百分比1.0-8.0wt%氧化铋、18.0-70.0wt%氧化碲、15.0-65.0wt%氧化铅、1.0-3.0wt%氧化钠、2-8.0wt%五氧化二磷,1.0-12.0wt%氧化银,0-3.0wt%氧化硼中的几种。
4.根据权利要求2所述的硅粉改性晶体硅太阳能电池复合银电极浆料的制备方法,其特征在于:步骤1)所述的混合均匀,进行熔炼,然后取出,水淬、粉碎、球磨、过筛,干燥后过筛得到玻璃粉,用三维混料机将上述原料混合均匀后,装于铂金坩埚,置于高温电阻炉中进行熔炼,于900-1100℃熔炼1小时,取出后水淬、粉碎、球磨、过筛,于65-75℃干燥后过筛得到玻璃粉,D100≤1.8μm。
5.根据权利要求2所述的硅粉改性晶体硅太阳能电池复合银电极浆料的制备方法,其特征在于:步骤2)所述的树脂,为乙基纤维素、硝基纤维素、乙基羟乙基纤维素、木松香中的一种或多种,当混合时为任意比例;所述的有机溶剂,为萜品醇、松节油、二乙二醇丁醚、二乙二醇二丁醚、丁基卡必醇醋酸酯、二丙二醇单甲醚、三丙二醇单甲醚中的一种或多种,当混合时为任意比例;所述的分散剂,为表面活性剂司班85;所述的防沉剂,为有机膨润土。
6.根据权利要求2所述的硅粉改性晶体硅太阳能电池复合银电极浆料的制备方法,其特征在于:步骤2)称取,按照4.0-15.0wt%树脂、78.0-88.0wt%有机溶剂、4.0-8.0wt%分散剂、2.0-6.0wt%防沉剂来称取。
7.根据权利要求2所述的硅粉改性晶体硅太阳能电池复合银电极浆料的制备方法,其特征在于:步骤2)所述的将树脂溶于有机溶剂中,再加入分散剂和防沉剂作为助剂,搅拌均匀形成有机载体,是将有机溶剂加入不锈钢容器中混合,再在搅拌过程中加入树脂,升温至70-90℃,待树脂完全溶解完后,降温至40-50℃下加入表面活性剂和防沉剂,过滤得到透明的具有良好印刷性的有机载体。
8.根据权利要求2所述的硅粉改性晶体硅太阳能电池复合银电极浆料的制备方法,其特征在于:步骤3)所述的称取银粉、银包硅粉、玻璃粉添加到有机载体中,是称取5.0-40.0wt%银粉、50.0-85.0wt%银包硅粉、2.0-4.0wt%玻璃粉、0-1.6wt%金属氧化物粉,添加到6.0-18.0wt%有机载体中。
9.根据权利要求2所述的硅粉改性晶体硅太阳能电池复合银电极浆料的制备方法,其特征在于:步骤3)所述的粒径为0.5-1.6μm、振实密度为3.2-6.0g/cm3的类球形银粉;所述的银包硅粉,银含量为25.0-35.0%的粉体、粒径为0.1-0.6μm、振实密度为0.2-1.2g/cm3;所述银包硅粉中的硅粉采用射频感应等离子体制备技术制备;所述的金属氧化物粉,为氧化锌、三氧化二铋、氧化镁、氧化钠、氧化镍、氧化铜、氧化亚铜、二氧化锆的一种或几种混合,当混合时为任意比例。
10.根据权利要求2所述的硅粉改性晶体硅太阳能电池复合银电极浆料的制备方法,其特征在于:步骤3)所述的搅拌均匀,研磨,真空脱气,是用高速分散机搅拌均匀,使用三辊研磨机研磨3-4遍,使用细度测试仪测试细度小于5μm为止,再用搅拌脱泡机真空脱气。
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