CN109385235A - 锂电池耐电解液胶黏剂及制备方法及锂电池用胶带 - Google Patents
锂电池耐电解液胶黏剂及制备方法及锂电池用胶带 Download PDFInfo
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Abstract
本发明涉及锂电池用胶带,具体涉及锂电池耐电解液胶黏剂及其制备方法以及锂电池用胶带。一种锂电池耐电解液胶黏剂,包括20~50份的丙烯酸十八酯、1~10份的4‑甲基丙烯酰氧基乙基偏苯三酸酐、1~5份的丙烯腈、1~4份的四氢呋喃丙烯酸酯、0.001~0.5份的自由基引发剂过氧化马来酸叔丁酯、0.001~1份的三氯化铁、0.01~2份的三苯基磷、50~150份的有机溶剂、1~10份的环氧化聚丁二烯和0.1~1份固化促进剂;以上均为质量份数。本发明提升了胶带的在高温环境下耐电解液性能,解决了传统橡胶改性丙烯酸酯压敏胶相容性差的问题。本发明引入四氢呋喃丙烯酸酯功能单体,可进一步增强丙烯酸酯压敏胶在电解液中的粘合能力。
Description
技术领域
本发明涉及锂电池用胶带,具体涉及锂电池耐电解液胶黏剂及其制备方法以及锂电池用胶带。
背景技术
锂离子电池具有重量轻、储能大、功率大、无污染等特点,在各个领域的应用也越来越广泛,它的研究和生产都取得了飞速发展,锂离子电池在电动车上作为动力能源,成为了电动车发展的一个新趋势。在锂离子电池的组装生产过程中,一般使用专用胶带对锂离子电池的电芯,极耳以及终止部位进行固定、绝缘和保护。这种锂电池专用胶带通常采用高分子薄膜为基材,在此基础上涂上耐锂电池电解液专用胶水,厚度为5~50 mm。锂电池专用胶带通常要具有较好的抗拉强度高,粘性好,胶带揭开不留残胶,耐100℃高温,耐电解液(pH值:5.5~6.5),电气绝缘性高等性能。
锂电池专用胶带的种类较多,按主体材料主要分为丙烯酸酯、聚氨酯、热塑性弹性体和其他杂化体系等。丙烯酸酯类锂电池专用胶带是目前应用范围最广的压敏胶,具有良好的粘性,透明性好,优异的耐候性和耐热性,适用于锂电池领域。近年来,锂电池组装领域市场对耐电解液胶带有较大的需求。锂电池专用胶带在电池组装过程和后期应用过程中都会接触到锂离子电池的电解液,因此应用于锂离子电池的胶带需要耐受电解液及高温的长期浸泡。在高温电解液长期浸泡后依然保持足够的粘结性能(不低于85%),防止电解液的渗漏,并且不会有溶出物污染电解液。
电解液一般由高纯度的有机溶剂、电解质锂盐(六氟磷酸锂)、必要的添加剂等原料,在一定条件下,按一定比例配制而成的。有机溶剂是电解液的主体部分,电解液的性能与溶剂的性能密切相关。锂离子电池电解液中常用的溶剂有碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)等。丙烯酸酯类锂电池专用胶带由于聚合物极性较大,极易在有机溶剂电解液中溶胀而失去粘性,所以大多数丙烯酸酯类锂电池专用胶带耐电解液性能较差,易出现起皱和粘力变差现象。丙烯酸酯类锂电池专用胶带常需要进行改性才能部分满足耐高温要求。专利(CN 103911088 A)采用特定的几类丙烯酸单体进行组合聚合获得一种耐电解液丙烯酸酯压敏胶带。该专利使用的丙烯酸单体都是一些极性较高的单体,在长期充放电过程,极易在电解液中发生溶胀起皱现象。专利(CN103468177A)采用橡胶参杂改性丙烯酸酯类压敏胶带获得耐高温电解液压敏胶带。该专利难解橡胶与丙烯酸酯类压敏胶相容性问题,易出现相分离,胶带结构不均一问题。随着锂电池对组装使用的胶带厚度要求越来越薄,丙烯酸酯类压敏胶涂层变薄,耐电解液性能更差,无法满足应用要求。
发明内容
因此,本发明的第一目的在于提供一种耐电解液性能好、稳定性高的锂电池耐电解液胶黏剂。
本发明的目的是这样实现的。
一种锂电池耐电解液胶黏剂,包括20~50份的丙烯酸十八酯、1~10 份的4-甲基丙烯酰氧基乙基偏苯三酸酐、1~5 份的丙烯腈、1~4份的四氢呋喃丙烯酸酯、0.001~0.5份的自由基引发剂过氧化马来酸叔丁酯、0.001~1份的三氯化铁、0.01~2份的三苯基磷、50~150份的有机溶剂、1~10份的环氧化聚丁二烯和0.1~1份固化促进剂;以上均为质量份数。
上述技术方案还可作下述进一步完善。
所述的有机溶剂是乙酸乙酯,甲苯和乙酸丁酯中的一种或二种混合物或三种混合物。
所述环氧化聚丁二烯的环氧值为0.25~0.55 mol/100g及数均分子量为1000~2500。
所述固化促进剂为三乙醇胺、二甲基苯胺和2,4,6-三(二甲胺基甲基)苯酚中的一种或二种混合物或三种混合物。
本发明的第二目的在于提供一种耐电解液性能好、稳定性高的锂电池耐电解液胶黏剂制备方法。
本发明第二目的是这样实现的。
一种锂电池耐电解液胶黏剂制备方法,将20~50份的丙烯酸十八酯、1~10 份的4-甲基丙烯酰氧基乙基偏苯三酸酐、1~5 份的丙烯腈、1~4份的四氢呋喃丙烯酸酯、0.001~0.5份的自由基引发剂过氧化马来酸叔丁酯、0.001~1份的三氯化铁、0.01~2份的三苯基磷和50~150份的有机溶剂混合后,进行氮气除氧30~120分钟后,控温于60~120℃,在氮气保护下进行反向原子转移自由基聚合聚合反应1~20小时,数均分子量控制为10000~200000,分子量多分散系数控制为1.1~1.5,玻璃化转变温度控制在-45~20℃之间,反应温度降至10~30℃之间,再加入1~10份的环氧化聚丁二烯和0.1~1份固化促进剂进行混合后,获得锂电池耐电解液胶黏剂;以上均为质量份数。
本发明的第三目的在于提供一种耐电解液性能好、稳定性高的含有锂电池耐电解液胶黏剂的锂电池用胶带。
本发明第三目的是这样实现的。
一种锂电池用胶带,包括聚对苯二甲酸乙二醇酯薄膜层,含锂电池耐电解液胶黏剂层和隔离层。
隔离层设在聚对苯二甲酸乙二醇酯薄膜层正面,锂电池耐电解液胶黏剂层设在聚对苯二甲酸乙二醇酯薄膜层反面,然后收卷分切,得锂电池用胶带。锂电池耐电解液胶黏剂层组份为:20~50份的丙烯酸十八酯、1~10 份的4-甲基丙烯酰氧基乙基偏苯三酸酐、1~5份的丙烯腈、1~4份的四氢呋喃丙烯酸酯、0.001~0.5份的自由基引发剂过氧化马来酸叔丁酯、0.001~1份的三氯化铁、0.01~2份的三苯基磷、50~150份的有机溶剂、1~10份的环氧化聚丁二烯和0.1~1份固化促进剂;以上均为质量份数。
上述技术方案还可作下述进一步完善。
先将非硅隔离剂均匀涂布在1~50mm聚对苯二甲酸乙二醇酯薄膜层正面,然后置于80~120℃下,保温固化1~10 min,获得0.1~2 mm隔离层。
再将锂电池耐电解液胶黏剂均匀涂布在聚对苯二甲酸乙二醇酯薄膜层反面,然后置于80~130℃下,保温干燥固化1~60 min,获得1~30mm锂电池耐电解液胶黏剂层。
为了获得耐电解液胶黏剂,本发明选用极性低的丙烯酸十八酯为主体,引入酸酐单体和附着力单体,采用反向原子转移自由基聚合法(R-ARTP)聚合获得分子量分布较窄结构均一的胶黏剂,再加入极性低的环氧化聚丁二烯进行交联,提高内聚力和非极性,获得一种聚丁二烯交联改性丙烯酸酯压敏胶带。
本发明解决了传统丙烯酸酯压敏胶耐电解液性能差的问题。本发明选用非极性丙烯酸十八酯单体、酸酐功能单体和附着力单体进行反向原子转移自由基聚合(R-ARTP)聚合,合成了化学结构均一和分子量分布较窄的酸酐改性丙烯酸酯压敏胶。
为了进一步增强丙烯酸酯压敏胶的高温耐电解液性能,本发明采用非极性低分子量的环氧化聚丁二烯为交联剂,利用环氧官能团固化酸酐改性丙烯酸酯压敏胶,进一步提升了胶带的在高温环境下耐电解液性能。聚丁二烯通过化学交联网络分散于丙烯酸酯压敏胶体系上,解决了传统橡胶改性丙烯酸酯压敏胶相容性差的问题。
本发明引入四氢呋喃丙烯酸酯功能单体,可进一步增强丙烯酸酯压敏胶在电解液中的粘合能力。
附图说明
图1为实施例锂电池用胶带结构示意图。
具体实施方式
下面结合实施例对本发明作进一步详细的描述,但本发明的实施方式不限于此。以下实施例中所涉及的份数均是质量份数。
实施例一,其是一种锂电池专用耐电解液胶黏剂和耐电解液胶带,由以下步骤制备得到,步骤一 合成耐电解液胶黏剂,将45份的丙烯酸十八酯(SA)、4 份的4-甲基丙烯酰氧基乙基偏苯三酸酐(4-META)、1 份的丙烯腈(AN)、2份的四氢呋喃丙烯酸酯(THFA)、0.05份的自由基引发剂过氧化马来酸叔丁酯(TBMA)、0.1份的三氯化铁、0.2份的三苯基磷和100份的甲苯混合后,进行氮气除氧30分钟后,控温于90℃,在氮气保护下进行反向原子转移自由基聚合(R-ARTP)聚合反应5小时,数均分子量(Mn)控制为165000,分子量多分散系数控制为1.4,反应温度降至30℃,再加入4份的环氧化聚丁二烯(环氧值为0.54 mol/100g, 数均分子量为2066)和0.3份固化促进剂2,4,6-三(二甲胺基甲基)苯酚进行混合后,获得锂电池专用耐电解液胶黏剂;以上均为质量份数。
结合图1,步骤二 耐电解液胶带制备,先将非硅隔离剂RL-600均匀涂布在10 mm聚对苯二甲酸乙二醇酯薄膜层1正面,然后置于120℃下,保温固化5 min,获得0.4 mm隔离层2。
再将步骤一制备的锂电池专用耐电解液胶黏剂均匀涂布在聚对苯二甲酸乙二醇酯薄膜层1反面,然后置于120℃下,保温干燥固化5 min,获得4 mm锂电池专用耐电解液胶黏剂层3,收卷分切,获得锂电池专用耐电解液胶带。
实施例二,其是一种锂电池专用耐电解液胶黏剂和耐电解液胶带,由以下步骤制备得到,步骤一 合成耐电解液胶黏剂,将35份的丙烯酸十八酯(SA)、7 份的4-甲基丙烯酰氧基乙基偏苯三酸酐(4-META)、2份的丙烯腈(AN)、1份的四氢呋喃丙烯酸酯(THFA)、0.1份的自由基引发剂过氧化马来酸叔丁酯(TBMA)、0.2份的三氯化铁、0.3份的三苯基磷和80份的乙酸乙酯混合后,进行氮气除氧60分钟后,控温于80℃,在氮气保护下进行反向原子转移自由基聚合(R-ARTP)聚合反应10小时,数均分子量(Mn)控制为84000,分子量多分散系数控制为1.3,反应温度降至25℃,再加入7份的环氧化聚丁二烯(环氧值为0.28 mol/100g, 数均分子量为1414)和0.4份固化促进剂二甲基苯胺进行混合后,获得锂电池专用耐电解液胶黏剂;以上均为质量份数。
结合图1,步骤二耐电解液胶带制备,先将非硅隔离剂RL-600均匀涂布在20 mm 聚对苯二甲酸乙二醇酯薄膜层1正面,然后置于100℃下,保温固化7 min,获得0.8 mm隔离层2。
再将步骤一制备的锂电池专用耐电解液胶黏剂均匀涂布在聚对苯二甲酸乙二醇酯薄膜层1反面,然后置于110℃下,保温干燥固化10 min,获得6 mm锂电池专用耐电解液胶黏剂层3,收卷分切,获得锂电池专用耐电解液胶带。
实施例三,其是一种锂电池专用耐电解液胶黏剂和耐电解液胶带,由以下步骤制备得到,步骤一 合成耐电解液胶黏剂,将30份的丙烯酸十八酯(SA)、9份的4-甲基丙烯酰氧基乙基偏苯三酸酐(4-META)、1份的丙烯腈(AN)、2份的四氢呋喃丙烯酸酯(THFA)、0.3份的自由基引发剂过氧化马来酸叔丁酯(TBMA)、0.3份的三氯化铁、0.5份的三苯基磷和70份的乙酸乙酯混合后,进行氮气除氧100分钟后,控温于85℃,在氮气保护下进行反向原子转移自由基聚合(R-ARTP)聚合反应15小时,数均分子量(Mn)控制为48000,分子量多分散系数控制为1.2,反应温度降至20℃,再加入9份的环氧化聚丁二烯(环氧值为0.28 mol/100g, 数均分子量为1414)和0.6份固化促进剂三乙醇胺进行混合后,获得锂电池专用耐电解液胶黏剂;以上均为质量份数。
结合图1,步骤二 耐电解液胶带制备,先将非硅隔离剂RL-600均匀涂布在30 mm聚对苯二甲酸乙二醇酯薄膜层1正面,然后置于90℃下,保温固化3 min,获得0.2 mm隔离层2。
再将步骤一制备的锂电池专用耐电解液胶黏剂均匀涂布在聚对苯二甲酸乙二醇酯薄膜层1反面,然后置于130℃下,保温干燥固化20 min,获得3 mm锂电池专用耐电解液胶黏剂层3,收卷分切,获得锂电池专用耐电解液胶带。
实施例四,其是一种锂电池专用耐电解液胶黏剂和耐电解液胶带,由以下步骤制备得到,步骤一合成耐电解液胶黏剂,将20份的丙烯酸十八酯(SA)、6份的4-甲基丙烯酰氧基乙基偏苯三酸酐(4-META)、4份的丙烯腈(AN)、4份的四氢呋喃丙烯酸酯(THFA)、0.5份的自由基引发剂过氧化马来酸叔丁酯(TBMA)、0.5份的三氯化铁、0.8份的三苯基磷和60份的乙酸丁酯混合后,进行氮气除氧30分钟后,控温于85℃,在氮气保护下进行反向原子转移自由基聚合(R-ARTP)聚合反应15小时,数均分子量(Mn)控制为48000,分子量多分散系数控制为1.2,反应温度降至20℃,再加入9份的环氧化聚丁二烯(环氧值为0.54 mol/100g, 数均分子量为2066)和0.8份固化促进剂2,4,6-三(二甲胺基甲基)苯酚进行混合后,获得锂电池专用耐电解液胶黏剂;以上均为质量份数。
结合图1,步骤二耐电解液胶带制备,先将非硅隔离剂RL-600均匀涂布在40 mm 聚对苯二甲酸乙二醇酯薄膜层1正面,然后置于80℃下,保温固化2 min,获得1 mm隔离层2。
再将步骤一制备的锂电池专用耐电解液胶黏剂均匀涂布在聚对苯二甲酸乙二醇酯薄膜层1反面,然后置于125℃下,保温干燥固化7 min,获得8 mm锂电池专用耐电解液胶黏剂层3,收卷分切,获得锂电池专用耐电解液胶带。
本发明参照目前测试胶带的通用方法对以上的四种实施例得到的锂电池专用耐电解液胶带进行补粘性、180°剥离力和高温耐电解液性能指标测试。初粘性参照GB/T4852-2002标准进行测试。180°剥离力参照GB/T2792-2014标准进行测试。所有测试数据对比情况请见下表1。
表1 各实施例具体性能测试对照情况
从表1的数据可以看出,本发明制备的锂电池专用耐电解液胶带具有优良的耐电解液性能。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (5)
1.一种锂电池耐电解液胶黏剂,其特征在于:包括20~50份的丙烯酸十八酯、1~10 份的4-甲基丙烯酰氧基乙基偏苯三酸酐、1~5 份的丙烯腈、1~4份的四氢呋喃丙烯酸酯、0.001~0.5份的自由基引发剂过氧化马来酸叔丁酯、0.001~1份的三氯化铁、0.01~2份的三苯基磷、50~150份的有机溶剂、1~10份的环氧化聚丁二烯和0.1~1份固化促进剂;以上均为质量份数。
2.根据权利要求1所述的一种锂电池耐电解液胶黏剂,其特征在于:所述的有机溶剂是乙酸乙酯,甲苯和乙酸丁酯中的一种或二种混合物或三种混合物;
所述环氧化聚丁二烯的环氧值为0.25~0.55 mol/100g及数均分子量为1000~2500;
所述的固化促进剂为三乙醇胺、二甲基苯胺和2,4,6-三(二甲胺基甲基)苯酚中的一种或二种混合物或三种混合物。
3.一种锂电池耐电解液胶黏剂制备方法,特征在于:将20~50份的丙烯酸十八酯、1~10 份的4-甲基丙烯酰氧基乙基偏苯三酸酐、1~5 份的丙烯腈、1~4份的四氢呋喃丙烯酸酯、0.001~0.5份的自由基引发剂过氧化马来酸叔丁酯、0.001~1份的三氯化铁、0.01~2份的三苯基磷和50~150份的有机溶剂混合后,进行氮气除氧30~120分钟后,控温于60~120℃,在氮气保护下进行反向原子转移自由基聚合聚合反应1~20小时,数均分子量控制为10000~200000,分子量多分散系数控制为1.1~1.5,玻璃化转变温度控制在-45~20℃之间,反应温度降至10~30℃之间,再加入1~10份的环氧化聚丁二烯和0.1~1份固化促进剂进行混合后,获得锂电池耐电解液胶黏剂;以上均为质量份数。
4.一种锂电池用胶带,其特征在于:包括聚对苯二甲酸乙二醇酯薄膜层,含有权利要求1所述的锂电池耐电解液胶黏剂层和隔离层;
隔离层设在聚对苯二甲酸乙二醇酯薄膜层正面,含有权利要求1所述的锂电池耐电解液胶黏剂层设在聚对苯二甲酸乙二醇酯薄膜层反面,收卷分切,获得锂电池用胶带。
5.根据权利要求4所述锂电池用胶带,其特征在于:先将非硅隔离剂均匀涂布在1~50mm聚对苯二甲酸乙二醇酯薄膜层正面,然后置于80~120℃下,保温固化1~10 min,获得0.1~2 mm隔离层;
再将权利要求1的锂电池耐电解液胶黏剂均匀涂布在聚对苯二甲酸乙二醇酯薄膜层反面,然后置于80~130℃下,保温干燥固化1~60 min,获得1~30mm含有权利要求1所述的锂电池耐电解液胶黏剂层。
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