CN107887050A - 一种晶体硅太阳能电池高可焊性正面电极银浆及制备方法 - Google Patents
一种晶体硅太阳能电池高可焊性正面电极银浆及制备方法 Download PDFInfo
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- CN107887050A CN107887050A CN201711204656.5A CN201711204656A CN107887050A CN 107887050 A CN107887050 A CN 107887050A CN 201711204656 A CN201711204656 A CN 201711204656A CN 107887050 A CN107887050 A CN 107887050A
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- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 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
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种晶体硅太阳能电池高可焊性正面电极银浆及其制备方法,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、锡合金粉、石墨粉、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银浆。
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,具体涉及一种晶体硅太阳能电池高可焊性正面电极银浆及制备方法。
背景技术
晶体硅太阳能电池是目前应用率最高的太阳能电池,但因为其持续使用时间超过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,还必须要有与焊带的有效焊接性,能保证足够的焊接强度,因此,电极拥有高可焊性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、无机粘结材料、有机载体和添加剂组成,导电粉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,但银的价格相对较高,如何降低成本是当前需要解决的主要问题之一,针对这一问题,已有较多的研究成果,专利CN 104157331 A,CN103000250 A,CN102426872 A和CN106128550 A中,通过掺入银包铜作为导电相代替部分银粉,专利CN106876000 A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CN103650238 A,CN103596648 A,CN103545016 A,CN103545015 A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CN105810284 A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CN106297954 A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CN105655416 A,CN105810286 A,CN105810287 A,CN105655007 A,及CN105655010 A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CN106782755 A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CN103106952 A中用银粉、锡粉、银包镍粉、银包铜粉组成导电相。专利CN102426873 A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CN1070682441 A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。本发明的目的就是通过导电组分的配方改进,用锡合金粉和石墨粉代替部分银粉、易被氧化的镍、铜等金属粉或银包金属铝、镍、铜粉,其中石墨粉作为导电材料组分和氧化保护材料,既能解决银易迁移的问题,同时可焊性和附着力得到极大提高,因此本发明可制备出成本低、转换效率稳定、附着力良好,焊接性更优的正面电极银浆。
发明内容
本发明目的在于提供一种晶体硅太阳能电池高可焊性正面电极银浆及制备方法,用于替代目前纯金属粉作为导电相的高银含量浆料。
本发明所述的一种晶体硅太阳能电池高可焊性正面电极银浆,由以下组分组成:
银粉45.0-75.0wt%、锡合金粉5.0-25.0wt%、石墨粉1.0-15.0wt%、玻璃粉0.8-4.5wt%、0.1-1.5wt%金属氧化物粉、有机载体8.0-15.0wt%;
所述的银粉,优选粒径为0.8-1.8μm、振实密度为2.5-6.5g/cm3的类球形银粉;
所述的锡合金粉,优选粒径为0.6-1.0μm、振实密度为1.0-2.5g/cm3;所述锡合金粉采用射频感应等离子体制备技术制备;
所述的石墨粉,优选粒径为0.5-0.8μm的高纯石墨粉。
本发明还涉及上述的一种晶体硅太阳能电池高可焊性正面电极银浆的制备方法,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、锡合金粉、石墨粉、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银浆。
本发明步骤1)所述的称取原料,优选称取5.0-45.0wt%氧化铋、10.0-60.0wt%氧化碲、10.0-60.0wt%氧化铅、1.0-5.0wt%氧化锂、5.0-8.0wt%五氧化二磷,1.0-5.0wt%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,优选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950-1150℃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,优选为乙基纤维素、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,优选萜品醇、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,优选表面活性剂司班85;
所述的防沉剂,优选有机膨润土。
步骤2)所述的称取,按照5.0-12.0wt%树脂、84.0-90.0wt%有机溶剂、0.8-6.0wt%分散剂、0.2-2.0wt%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,优选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、锡合金粉、石墨粉、玻璃粉、金属氧化物粉添加到有机载体中,优选称取62.0-75.0wt%银粉、8.0-17.0wt%锡合金粉、3.0-10.0wt%石墨粉、0.3-1.5wt%玻璃粉、0.3-1.5wt%金属氧化物粉,添加到8.0-15.0wt%有机载体中;
步骤3)所述的银粉,优选粒径为0.8-1.8μm、振实密度为2.5-6.5g/cm3的类球形银粉;
所述的锡合金粉,优选粒径为0.6-1.0μm、振实密度为1.0-2.5g/cm3;所述锡合金粉采用射频感应等离子体制备技术制备;
所述的石墨粉,优选粒径为0.5-0.8μm的高纯石墨粉。
所述的金属氧化物粉,优选氧化锌,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,优选用高速分散机搅拌均匀,使用三辊研磨机研磨6-10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,丝网印刷质量优:400目不锈钢丝网印刷,线宽≤24μm(用膜厚仪测试)。
2、光电转换效率高:单晶硅片≥21%,多晶硅片≥20%,(太阳能模拟器在标准条件下测试)。
3、本发明因通过添加锡合金粉作为金属导电项,在较高温度时,电极材料因烧结而结构变化,锡合金变为液体并在外力作用下有效填充银颗粒的间隙,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,同时因电极材料含锡合金而与含锡焊带能实现良好的焊接,焊接性能良好,用350℃烙铁手动将焊带焊接在电极上,用180°的拉力仪,以0.3cm/s的速度进行剥离,测试焊接拉力,附着力≥10.5N/mm2。
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5.0wt%氧化铋,20.0wt%氧化碲,60.0wt%氧化铅,5.0wt%氧化锂,8.0wt%五氧化二磷,2.0wt%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950℃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0.3-1.5μm;
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,12.0wt%乙基纤维素,2.0wt%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、锡合金粉和高纯石墨粉。特选形状包含平均粒径为1.8μm的类球形银粉,其振实密度6.5g/cm3;平均粒径为0.6μm的锡合金粉,振实密度为1.0g/cm3;平均粒径为0.5μm的石墨粉;以上导电粉体按照重量比75:11:3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。
步骤D:制备电极浆料。按质量百分比75.0%的导电银粉,11.0%的锡合金粉,3.0%的石墨粉,1.0%的金属氧化物粉(金属氧化物为氧化钛,氧化铋,氧化硼,氧化锌,二氧化硅,氧化铜,氧化镁,氧化铝,氧化镧的任意比例混合),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;
丝网印刷:400目不锈钢丝网印刷,线宽≤24μm;
可焊性良好;
转换效率:单晶硅片≥21%,多晶硅片≥20%;
附着力:≥10.6N/mm2。
实施例2:
步骤A:称取45.0wt%氧化铋,10.0wt%氧化碲,34.0wt%氧化铅,1.0wt%氧化锂,5.0wt%五氧化二磷,5.0wt%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1150℃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,5.0wt%乙基纤维素,6.0wt%的表面活性剂司班85,0.2wt%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、锡合金粉和高纯石墨粉。特选形状包含平均粒径为0.8μm的类球形银粉,其振实密度2.5g/cm3;平均粒径为1.0μm的锡合金粉,振实密度为2.5g/cm3;平均粒径为0.8μm的石墨粉;以上导电粉体按照重量比72:12:1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。
步骤D:制备电极浆料。按质量百分比62.0%的导电银粉,17.0%的锡合金粉,4.2%的石墨粉,0.3%的金属氧化物粉(金属氧化物为氧化钛,氧化铋,氧化硼,氧化锌,二氧化硅,氧化铜,氧化镁,氧化铝,氧化镧的任意比例混合),1.5%的玻璃粉,15.0%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;
丝网印刷:400目不锈钢丝网印刷,线宽≤24μm;
可焊性良好;
转换效率:单晶硅片≥21%,多晶硅片≥20%;
附着力:≥12.5N/mm2。
实施例3:
步骤A:称取20.0wt%氧化铋,60.0wt%氧化碲,10.0wt%氧化铅,3.0wt%氧化锂,6.0wt%五氧化二磷,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1050℃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,6.2wt%乙基纤维素、2.0wt%硝基纤维素,2.0wt%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、锡合金粉和高纯石墨粉。特选形状包含平均粒径为1.2μm的类球形银粉,其振实密度4.2g/cm3;平均粒径为0.8μm的锡合金粉,振实密度为2.0g/cm3;平均粒径为0.6μm的石墨粉;以上导电粉体按照重量比72:12:1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。
步骤D:制备电极浆料。按质量百分比66.0%的导电银粉,8.0%的锡合金粉,10.0%的石墨粉,1.5%的金属氧化物粉(金属氧化物为氧化钛,氧化铋,氧化硼,氧化锌,二氧化硅,氧化铜,氧化镁,氧化铝,氧化镧的任意比例混合),4.5%的玻璃粉,10.0%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;
丝网印刷:400目不锈钢丝网印刷,线宽≤24μm;
可焊性良好;
转换效率:单晶硅片≥21%,多晶硅片≥20%;
附着力:≥12N/mm2。
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)
1.一种晶体硅太阳能电池高可焊性正面电极银浆,其特征在于,由以下组分组成:
银粉45.0-75.0wt%、锡合金粉5.0-25.0wt%、石墨粉1.0-15.0wt%、玻璃粉0.8-4.5wt%、0.1-1.5wt%金属氧化物粉、有机载体8.0-15.0wt%;
所述的银粉,粒径为0.8-1.8μm、振实密度为2.5-6.5g/cm3的类球形银粉;
所述的锡合金粉,粒径为0.6-1.0μm、振实密度为1.0-2.5g/cm3;所述锡合金粉采用射频感应等离子体制备技术制备;
所述的石墨粉,粒径为0.5-0.8μm的高纯石墨粉。
2.权利要求1所述的一种晶体硅太阳能电池高可焊性正面电极银浆的制备方法,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、锡合金粉、石墨粉、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银浆。
3.根据权利要求2所述的一种晶体硅太阳能电池高可焊性正面电极银浆的制备方法,其特征在于:步骤1)所述的称取原料,是称取质量百分比5.0-45.0wt%氧化铋、10.0-60.0wt%氧化碲、10.0-60.0wt%氧化铅、1.0-5.0wt%氧化锂、5.0-8.0wt%五氧化二磷,1.0-5.0wt%氧化硼中的几种。
4.根据权利要求2所述的一种晶体硅太阳能电池高可焊性正面电极银浆的制备方法,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950-1150℃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所述的一种晶体硅太阳能电池高可焊性正面电极银浆的制备方法,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所述的一种晶体硅太阳能电池高可焊性正面电极银浆的制备方法,其特征在于:步骤2)称取,按照5.0-12.0wt%树脂、84.0-90.0wt%有机溶剂、0.8-6.0wt%分散剂、0.2-2.0wt%防沉剂来称取。
7.根据权利要求2所述的一种晶体硅太阳能电池高可焊性正面电极银浆的制备方法,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所述的一种晶体硅太阳能电池高可焊性正面电极银浆的制备方法,其特征在于:步骤3)所述的称取银粉、锡合金粉、石墨粉、玻璃粉、金属氧化物粉添加到有机载体中,称取62.0-75.0wt%银粉、8.0-17.0wt%锡合金粉、3.0-10.0wt%石墨粉、0.3-1.5wt%玻璃粉、0.3-1.5wt%金属氧化物粉,添加到8.0-15.0wt%有机载体中。
9.根据权利要求2所述的一种晶体硅太阳能电池高可焊性正面电极银浆的制备方法,其特征在于:步骤3)所述的银粉,粒径为0.8-1.8μm、振实密度为2.5-6.5g/cm3的类球形银粉;所述的锡合金粉,粒径为0.6-1.0μm、振实密度为1.0-2.5g/cm3;所述锡合金粉采用射频感应等离子体制备技术制备;所述的石墨粉,粒径为0.5-0.8μm的高纯石墨粉。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所述的一种晶体硅太阳能电池高可焊性正面电极银浆的制备方法,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6-10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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