CN105602497B - 聚氨酯改性丙烯酸类水性粘结剂及其制备方法和应用 - Google Patents
聚氨酯改性丙烯酸类水性粘结剂及其制备方法和应用 Download PDFInfo
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Abstract
一种聚氨酯改性丙烯酸类水性粘结剂,其特征在于该粘结剂采用聚乙二醇和二异氰酸酯反应,然后加入丙烯酸单体或甲基丙烯酸单体作为改性单体,在引发剂作用下与羟基丙烯酸树脂单体反应,获得乳液,该乳液即为粘结剂。本发明还公开了该粘结剂的制备方法和应用。与现有技术相比,本发明的优点在于:抗氧化能力和抗高电压的能力提高,同时与铝箔具有良好的粘结性能。
Description
技术领域
本发明涉及一种粘结剂,还涉及该粘结剂的制备方法,该粘结剂可以应用于锂离子电池中。
背景技术
随着智能手机以及数码相机等移动电子设备市场的扩大,可反复充放电、高容量的锂离子二次电池的市场也逐年扩大。锂离子电池性能受到电池材料、工艺以及使用环境等多方面因素的影响,其中制备电极时所使用的粘结剂的影响不容小觑。粘结剂起到粘结活性物质、导电剂,并将其粘附到集流体,形成完整电极结构的作用。同时粘结剂也会影响极片的柔韧性、极片在电解液中的溶胀性、电化学稳定性等诸多性能。
根据使用溶剂的不同粘结剂可分为油系和水系两大类。油系粘结剂以聚偏氟乙烯(PVDF)为代表,采用甲基吡咯烷酮(NMP)作为溶剂,可应用于二次电池的正极与及负极材料。但其电子和离子导电性差;有机溶剂NMP具有良好的分散性,但易挥发、易燃易爆、且毒性大。采用PVDF作粘结剂的极片涂布工艺要求密封,生产成本高。另一方面由于PVDF中含有氟,容易与嵌锂石墨等发生反应,导致锂离子电池性能下降。PVDF作为锂电池粘结剂的相关文献可以参考申请号为201410842426.1的中国发明专利申请公开《一种锂电池粘结剂专用聚偏氟乙烯的制备方法》(公开号为CN104530276A);201410515819.1的中国发明专利申请公开《一种导电聚合物交联的锂电池用粘结剂及其制备方法》(公布号为CN104282912A);申请号为201410519423.4的中国发明专利申请公开《一种碳材料填充的锂电池用粘结剂及其制备方法》(公开号为CN104269558A)等。
近年,从降低成本、控制环境污染以及提高电池性能方面考虑,丁苯橡胶(SBR)类以及聚丙烯酸类水性粘结剂逐渐取代PVDF成为负极粘结剂市场的主流,市场占有率达到70%左右。这类粘结剂的专利文献可以参考申请号为201510014203.0的中国发明专利申请公开《一种高功率锂离子电池负极粘结剂组合物及其制造方法》(公开号为CN104617302A);还可以参考申请号为201510160761.8的中国发明专利申请公开《一种锂离子电池负极粘结剂、负极以及电池》(公开号为CN104877593A)。
根据日本瑞翁(ZEON)公司的研究结果,SBR水性粘结剂在负极使用时非常稳定,但当用于正极时,由于其抗氧化性能差,在不断的充放电循环过程中,粘结剂在高电压状态下逐渐失效,从而影响电池的充放电性能和循环特性。
发明内容
本发明所要解决的技术问题是针对上述的技术现状而另外提供一种聚氨酯改性丙烯酸类水性粘结剂。
本发明所要解决的又一个技术问题是提供一种适合于锂离子电池正极极片的聚氨酯改性丙烯酸类水性粘结剂。
本发明所要解决的又一个技术问题是提供一种适合于锂离子电池正极极片的聚氨酯改性丙烯酸类水性粘结剂的制备方法。
本发明解决上述技术问题所采用的技术方案为:一种聚氨酯改性丙烯酸类水性粘结剂,其特征在于该粘结剂采用聚乙二醇和二异氰酸酯反应,然后加入丙烯酸单体或甲基丙烯酸单体作为改性单体,反应得到聚氨酯丙烯酸酯,在引发剂作用下与羟基丙烯酸树脂单体反应,获得乳液,该乳液即为粘结剂,前述聚乙二醇、二异氰酸酯、丙烯酸单体或甲基丙烯酸单体摩尔比满足1:1.6~2.3:1.9~2.3,前述聚氨酯丙烯酸酯与羟基丙烯酸树脂单体摩尔比为1:0.9~1.5。
一种聚氨酯改性丙烯酸类水性粘结剂的制备方法,其特征在于包括如下步骤:
①在反应器中加入聚乙二醇,氮气保护下加入二异氰酸酯,采用极性溶剂,60~90℃反应1~5小时,降温到45~55℃以下,加入丙烯酸单体或甲基丙烯酸单体,继续反应,得到聚氨酯丙烯酸酯混合液,上述聚乙二醇、二异氰酸酯及丙烯酸单体或甲基丙烯酸单体摩尔比满足1:1.6~2.3:1.9~2.3;
②将羟基丙烯酸树脂单体中滴加引发剂和步骤①中得到的聚氨酯丙烯酸酯混合液,搅拌下温度上升到70-85℃,反应1-5小时,加入碱液调整pH值至7~8,加水,搅拌后乳化,得到乳液,该乳液即为粘结剂,上述聚氨酯丙烯酸酯与羟基丙烯酸树脂单体摩尔比为1:0.9~1.5。
所述的丙烯酸单体或甲基丙烯酸单体可以是CH3CH2CHCOOCH3、CH3CH2CCOOCH2CH3、CH2CHCOOH、CH2CHCOOCH3、CH2CHCOOCH2CH3、CH2C(CH3)COOH或CH2CH(CH3)COOCH2CH2OH。
作为优选,所述的丙烯酸单体或甲基丙烯酸单体采用滴加方式进行,所述的丙烯酸单体或甲基丙烯酸单体采用一次性加入或分批次加入。
作为优选,步骤②中所述的引发剂为过硫酸铵,添加量为丙烯酸单体或甲基丙烯酸单体的0.1~0.4wt%。
将柔性的PEG链段引入,提高了极片的柔韧性,但PEG的分子量降低,粘结剂分子内部的交联密度增大,不利于拉伸。本发明中聚乙二醇可以采用PEG800或PEG400。
步骤①中所述的极性溶剂可以是乙醇、异丙醇、正丁醇或水。
与现有技术相比,本发明的优点在于:结合聚丙烯酸类树脂和聚氨酯,使其具有抗氧化能力和抗高电压的能力强的优点,同时,柔韧性好,分子链中含有异氰基(-NCO)和氨基甲酸酯基(-NH-COO-),故聚氨酯胶粘剂表现出高度的极性,与铝箔具有良好的粘结性能。
具体实施方式
以下结合实施例对本发明作进一步详细描述。
实施例1,第一步,聚氨酯丙烯酸脂的制备
在反应釜中加入聚乙二醇(PEG800),氮气保护下,加入二异氰酸酯(TDI),80℃下反应2hrs,降温到50℃摄氏度下,一次性加入甲基丙烯酸羟乙酯(HEMA),反应3hrs,得到聚氨酯-丙烯酸的溶液。投料摩尔比例为PEG:TDI:HEMA=1:2:2.1。本实施例中用到的溶剂为异丙醇。
第二步,聚氨酯-聚丙烯酸树脂合成
将羟基丙烯酸树脂单体滴加入过硫酸铵(添加量为HEMA的0.2wt%)以及第一步合成的聚氨酯丙烯酸酯的混合液中,搅拌下将温度升到80℃,反应3hrs,加入碱液调整pH值到7-8,然后继续加入水,搅拌30min,乳化,得到乳液。聚氨酯丙烯酸酯与羟基丙烯酸单体的摩尔比为1:1.2。
第三步锂离子电池浆料的制作
磷酸铁锂:乙炔黑:粘结剂=96:2:2的重量比混合,加水后配制成固含量为65-75%的浆料,高速搅拌4hrs,得到锂离子电池正极浆料。将浆料在铝箔上涂敷,40℃烘干24hrs,测试成膜的剥离强度。剥离强度为2.57N/m
实施例2,第一步,聚氨酯丙烯酸脂的制备
在反应釜中加入聚乙二醇(PEG400),氮气保护下,加入二异氰酸酯(TDI),90℃下反应1hrs;降温到45℃摄氏度下,滴加剩余的甲基丙烯酸甲酯,3hrs内滴加完成,得到聚氨酯-丙烯酸的溶液。投料摩尔比例为PEG:TDI:HEMA=1:2:2.1。本实施例中用到的溶剂为异丙醇。
第二步,聚氨酯-聚丙烯酸树脂合成
将羟基丙烯酸树脂单体滴加入过硫酸铵(添加量为羟基丙烯酸单体的0.2wt%)以及第一步合成的聚氨酯丙烯酸酯的混合液中,搅拌下将温度升到80℃,反应3hrs,加入碱液调整pH值到7-8,然后继续加入水,搅拌30min,乳化,得到乳液。聚氨酯丙烯酸酯与羟基丙烯酸单体的摩尔比为1:1.2。
第三步锂离子电池浆料的制作
磷酸铁锂:乙炔黑:粘结剂=96:2:2的重量比混合,加水后配制成固含量为65-75%的浆料,高速搅拌4hrs,得到锂离子电池正极浆料。将浆料在铝箔上涂敷,40℃烘干24hrs,测试成膜的剥离强度。剥离强度为3.29N/m
实施例3,第一步,聚氨酯丙烯酸脂的制备
在反应釜中加入聚乙二醇(PEG400),氮气保护下,加入二异氰酸酯(TDI),60℃下反应5hrs;降温到55℃摄氏度下,滴加剩余的乙基丙烯酸羟乙酯,3hrs内滴加完成,得到聚氨酯-丙烯酸的溶液。投料摩尔比例为PEG:TDI:HEMA=1:2:2.1。本实施例中用到的溶剂为异丙醇。
第二步,聚氨酯-聚丙烯酸树脂合成
将羟基丙烯酸树脂单体滴加入过硫酸铵(羟基丙烯酸单体的0.2wt%)以及第一步合成的聚氨酯丙烯酸酯的混合液中,搅拌下将温度升到80℃,反应3hrs,加入碱液调整pH值到7-8,然后继续加入水,搅拌30min,乳化,得到乳液。聚氨酯丙烯酸酯与羟基丙烯酸单体的摩尔比为1:1.2。
第三步锂离子电池浆料的制作
磷酸铁锂:乙炔黑:粘结剂=96:2:2的重量比混合,加水后配制成固含量为65-75%的浆料,高速搅拌4hrs,得到锂离子电池正极浆料。将浆料在铝箔上涂敷,40℃烘干24hrs,测试成膜的剥离强度。剥离强度为2.20N/m
负极材料制备,取该聚丙烯酸-聚氨酯锂离子电池粘结剂、导电炭黑及负极材料,碾磨搅拌均匀后加水调整固含量至50%至65%,得到浆料,此浆料经过筛网过滤后涂覆于铜箔上,于真空烘箱中烘烤6~24小时,烘烤温度为80℃~120℃,烘干后即制得负极极片;上述原料重量配比如下:粘结剂:导电贪黑:负极材料=1~3%:1~7%:90-98%。剥离强度为2.4N/m。实施例4,第一步,聚氨酯丙烯酸脂的制备
在反应釜中加入聚乙二醇(PEG800),氮气保护下,加入二异氰酸酯(TDI),90℃下反应1.5hrs,降温到55℃摄氏度下,一次性加入甲基丙烯酸羟乙酯(HEMA),反应3hrs,得到聚氨酯-丙烯酸的溶液。投料摩尔比例为PEG:TDI:HEMA=1:1.6:2.3。本实施例中用到的溶剂为乙醇。
第二步,聚氨酯-聚丙烯酸树脂合成
将羟基丙烯酸树脂单体滴加入过硫酸铵(添加量为HEMA的0.4wt%)以及第一步合成的聚氨酯丙烯酸酯的混合液中,搅拌下将温度升到70℃,反应5hrs,加入碱液调整pH值到7~8,然后继续加入水,搅拌30min,乳化,得到乳液。聚氨酯丙烯酸酯与羟基丙烯酸单体的摩尔比为1:0.9。
实施例5,第一步,聚氨酯丙烯酸脂的制备
在反应釜中加入聚乙二醇(PEG400),氮气保护下,加入二异氰酸酯(TDI),60℃下反应5hrs,降温到55℃摄氏度下,一次性加入甲基丙烯酸羟乙酯(HEMA),反应3hrs,得到聚氨酯-丙烯酸的溶液。投料摩尔比例为PEG:TDI:HEMA=1:2.3:1.9。本实施例中用到的溶剂为异丙醇。
第二步,聚氨酯-聚丙烯酸树脂合成
将羟基丙烯酸树脂单体滴加入过硫酸铵(添加量为HEMA的0.2wt%)以及第一步合成的聚氨酯丙烯酸酯的混合液中,搅拌下将温度升到85℃,反应2hrs,加入碱液调整pH值到7~8,然后继续加入水,搅拌30min,乳化,得到乳液。聚氨酯丙烯酸酯与羟基丙烯酸单体的摩尔比为1:1.5。
实施例6,第一步,聚氨酯丙烯酸脂的制备
在反应釜中加入聚乙二醇(PEG800),氮气保护下,加入二异氰酸酯(TDI),80℃下反应2hrs,降温到50℃摄氏度下,一次性加入CH3CH2CCOOCH2CH3,反应3hrs,得到聚氨酯-丙烯酸的溶液。投料摩尔比例为PEG:TDI:HEMA=1:2:2.2。本实施例中用到的溶剂为异丙醇。
第二步,聚氨酯-聚丙烯酸树脂合成
将羟基丙烯酸树脂单体滴加入过硫酸铵(添加量为HEMA的0.1wt%)以及第一步合成的聚氨酯丙烯酸酯的混合液中,搅拌下将温度升到80℃,反应3hrs,加入碱液调整pH值到7-8,然后继续加入水,搅拌30min,乳化,得到乳液。聚氨酯丙烯酸酯与羟基丙烯酸单体的摩尔比为1:1.0。
Claims (7)
1.一种聚氨酯改性丙烯酸类水性粘结剂,其特征在于该粘结剂采用聚乙二醇和二异氰酸酯反应,然后加入丙烯酸单体或甲基丙烯酸单体作为改性单体,反应得到聚氨酯丙烯酸酯,在引发剂作用下与羟基丙烯酸树脂单体反应,获得乳液,该乳液即为粘结剂,前述聚乙二醇、二异氰酸酯、丙烯酸单体或甲基丙烯酸单体摩尔比满足1:1.6~2.3:1.9~2.3,前述聚氨酯丙烯酸酯与羟基丙烯酸树脂单体摩尔比为1:0.9~1.5。
2.一种聚氨酯改性丙烯酸类水性粘结剂的制备方法,其特征在于包括如下步骤:
①在反应器中加入聚乙二醇,氮气保护下加入二异氰酸酯,采用极性溶剂,60~90℃反应1~5小时,降温到45~55℃以下,加入丙烯酸单体或甲基丙烯酸单体,继续反应,得到聚氨酯丙烯酸酯混合液,上述聚乙二醇、二异氰酸酯及丙烯酸单体或甲基丙烯酸单体摩尔比满足1:1.6~2.3:1.9~2.3;
②将羟基丙烯酸树脂单体中滴加引发剂和步骤①中得到的聚氨酯丙烯酸酯混合液,搅拌下温度上升到70~85℃,反应1~5小时,加入碱液调整pH值至7~8,加水,搅拌后乳化,得到乳液,该乳液即为粘结剂,上述聚氨酯丙烯酸酯与羟基丙烯酸树脂单体摩尔比为1:0.9~1.5。
3.根据权利要求2所述的聚氨酯改性丙烯酸类水性粘结剂的制备方法,其特征在于所述的丙烯酸单体或甲基丙烯酸单体采用滴加方式进行,所述的丙烯酸单体或甲基丙烯酸单体采用一次性加入或分批次加入。
4.根据权利要求2所述的聚氨酯改性丙烯酸类水性粘结剂的制备方法,其特征在于步骤②中所述的引发剂为过硫酸铵,添加量为丙烯酸单体或甲基丙烯酸单体的0.1~0.4wt%。
5.根据权利要求2所述的聚氨酯改性丙烯酸类水性粘结剂的制备方法,其特征在于所述的聚乙二醇采用PEG800或PEG400。
6.根据权利要求2所述的聚氨酯改性丙烯酸类水性粘结剂的制备方法,其特征在于步骤①中所述的极性溶剂为乙醇、异丙醇、正丁醇或水。
7.权利要求1所述的粘结剂在锂离子电池的正极和负极浆料制备中的应用。
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PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Polyurethane modified acrylic water-based adhesive and its preparation method and application Granted publication date: 20180109 Pledgee: Zhejiang Zhoushan Putuo Rural Commercial Bank Co.,Ltd. Donggang sub branch Pledgor: ZHEJIANG CASNOVO MATERIALS CO.,LTD. Registration number: Y2024330001380 |