CN115632210A - 一种荧光聚氨酯锂电池隔膜及其制备方法、锂电池 - Google Patents

一种荧光聚氨酯锂电池隔膜及其制备方法、锂电池 Download PDF

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CN115632210A
CN115632210A CN202211348144.7A CN202211348144A CN115632210A CN 115632210 A CN115632210 A CN 115632210A CN 202211348144 A CN202211348144 A CN 202211348144A CN 115632210 A CN115632210 A CN 115632210A
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余斌斌
田振
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Abstract

本发明公开了一种荧光聚氨酯锂电池隔膜及锂电池，其原料包括多异氰酸酯、大分子多元醇、小分子多元醇扩链剂、催化剂以及自制荧光碳点。荧光碳点为隔膜提供了荧光性能，对Fe2+、Fe3+有特异性猝灭效应，可用于检测电池内部铁离子含量，聚氨酯的结构可设计性大大拓展了聚氨酯隔膜的适用性；采用静电纺丝技术将荧光聚氨酯基体纺制成隔膜，并将其应用在锂电池中，制备锂电池。

Description

一种荧光聚氨酯锂电池隔膜及其制备方法、锂电池
技术领域
本发明涉及锂电池隔膜技术领域，尤其涉及一种荧光聚氨酯锂电池隔膜及其制备方法、锂电池。
背景技术
锂离子电池具有能量密度高、使用时间长和便携等优点，广泛应用于手机、电脑、数码相机、无人机、机器人和运动手环等电子设备中。与此同时，锂离子电池也是新能源汽车领域的主要的储能装置。锂离子电池由正负极、电解液和隔膜组成。隔膜是锂电池的重要组成部分，它直接决定了锂电池的性能。它的主要作用是隔离正负电极以防止短路，同时允许离子在两极之间自由通过并防止电子自由通过，是电池容量、循环性能和安全性能的重要决定因素。现如今隔膜需求不仅仅是性能的提升和安全性要求，同时提升隔膜的功能性和也成为动力锂电池隔膜的重要研究方向。
聚氨酯(PU)是一种环境友好且廉价的嵌段共聚物，因此近年来引起了人们的极大关注。它的结构包含硬段和软段，硬段提供了聚氨酯的空间稳定性，软段提供了聚氨酯的柔韧性，基于这种软硬相间的结构，聚氨酯具有突出的机械强度、优异的热稳定性、良好的电化学性能和易成膜能力。除此之外，聚氨酯结构的可设计性，更是赋予了聚氨酯多样化的功能性，可在聚氨酯链段中引入功能化结构或粒子，从而制备功能化聚氨酯。
发明内容
针对现有技术的不足，本发明提供了一种荧光聚氨酯锂电池隔膜及其制备方法，所述的荧光聚氨酯隔膜，以荧光碳点作为荧光添加剂，聚氨酯为基体，采用静电纺丝技术制备荧光聚氨酯锂电池隔膜，以及将所制备的荧光聚氨酯隔膜应用于锂电池中。
本发明提供一种荧光聚氨酯锂电池隔膜，所述荧光聚氨酯电池隔膜的原料包括多异氰酸酯、大分子多元醇、小分子多元醇和/或多元胺扩链剂、催化剂以及荧光碳点。
荧光碳点提供了体系所需的荧光性能，其是一种无毒无污染，对环境友好且合成路径简单、发光强度高的荧光剂，可轻松分散在各种溶剂中。将其引入聚氨酯中，赋予荧光特性时不破坏聚氨酯原有性能，得到兼具多种优势的荧光聚氨酯树脂。
所述荧光碳点的合成原料包括尿素、柠檬酸、乙二胺，其中，尿素质量分数为20％-30％，柠檬酸质量分数为35％-50％，乙二胺质量分数为20％-60％。合成荧光碳点步骤如下：取不同质量比的柠檬酸、尿素溶于盛有乙二胺的烧杯中，加入适量去离子水，烧杯用保鲜膜封口，于微波炉中高火微波5min，得到棕色溶液，然后使用500-1000d透析袋透析72h，冷冻干燥得到棕色荧光碳点粉末。
优选地，所述多异氰酸酯为异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、甲苯二异氰酸酯(TDI)、4,4'-二苯基甲烷二异氰酸酯(MDI)、4,4'-二环己基甲烷二异氰酸酯(HMDI)中的一种或多种；所述大分子多元醇为聚酯二元醇、聚醚二元醇、聚醚聚酯二元醇中的一种或多种；所述小分子多元醇或多元胺扩链剂为1,4-丁二醇、一缩二乙二醇、乙二胺、水合肼中的一种或多种。
优选地，所述荧光型聚氨酯的合成步骤为：
S1：将大分子多元醇加热到100℃，负压环境下脱水；
S2：向S1经脱水制得的大分子多元醇中加入多异氰酸酯,在75-95℃环境下搅拌反应3.5h，搅拌转速为400r/min；
S3：降温至50℃，加入扩链剂，升温至70-80℃，搅拌反应1h；
S4：再降温至50℃，加入催化剂与荧光碳点，升温至60-70℃，催化反应4h；
S5：将S4制得的树脂倒在PTFE(聚四氟乙烯)板上，室温成膜储存；
其中，整个反应过程中，使用有机溶剂进行黏度调节。
优选地，所述有机溶剂为丙酮、乙酸乙酯、N,N-二甲基甲酰胺、N-甲基吡咯烷酮中的一种或多种；
优选地，所述荧光聚氨酯锂电池隔膜的制备方法是将荧光聚氨酯溶于有机溶剂中，获得聚氨酯溶液，再将所述溶液通过静电纺丝机纺成膜，即可得荧光聚氨酯锂电池隔膜。
本发明进一步提出一种锂电池，其组成包括正极片、负极片、电解液以及所制备的荧光聚氨酯锂电池隔膜。
与现有技术相比，本发明有以下优点：
(1)本发明提供的一种荧光聚氨酯锂电池隔膜，具有荧光性能，对Fe2+、Fe3+有特异性猝灭效应，可用于检测电池内部铁离子含量。
(2)本发明提供的一种荧光聚氨酯锂电池隔膜中，聚氨酯的结构可设计性强，根据不同的应用需要，设计不同强度、韧性以及不同纤维粗细和孔隙率的锂电池隔膜。
(3)通过调节静电纺丝机不同参数，可设计性的制备不同纤维粗细、不同孔隙率等物理性质的隔膜。
附图说明
图1为本发明所制备荧光碳点的结构示意图，
图2为本发明实施例1所制备荧光碳点的红外光谱图，
图3为本发明实施例1所制备荧光碳点的TEM(透射电子显微镜)。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
一种荧光聚氨酯锂电池隔膜，首先取3g柠檬酸、4g尿素溶于盛有3g乙二胺的烧杯中，加入适量去离子水，烧杯用保鲜膜封口，于微波炉中高火微波5min，得到棕色溶液，再使用500-1000d透析袋透析72h，冷冻干燥得到棕色荧光碳点粉末。
将30g聚氧化丙烯二醇(Mn＝2000)加热到100℃，负压环境下脱水1h；再加入13.33g异佛尔酮二异氰酸酯在90℃环境下搅拌反应3.5h，搅拌转速为400r/min；降温至50℃，加入1.39g的1,4-丁二醇进行扩链，升温至80℃，搅拌反应1h；降温至50℃，加入T9、T12催化剂与荧光碳点，升温至60-70℃，催化反应4h；整个反应过程中，使用丙酮进行黏度调节，反应结束置于PTFE板上，室温成膜。
将荧光聚氨酯膜溶于有机溶剂中，获得聚氨酯溶液，再将所述溶液通过静电纺丝机纺成膜，即得荧光聚氨酯锂电池隔膜。
对上述所制备的荧光碳点进行红外光谱检测，得到如图1所示的红外光谱图，由此光谱图能够得到：
对所制备的荧光碳点进行投射电子显微镜分析，得到图2能够看出：
以正极片、负极片、电解液以及所制备的荧光聚氨酯锂电池隔膜为主要原料，组装锂电池。
实施例2
一种荧光聚氨酯锂电池隔膜，首先取0.5g柠檬酸、3.5g尿素溶于盛有6g乙二胺的烧杯中，加入适量去离子水，烧杯用保鲜膜封口，于微波炉中高火微波5min，得到棕色溶液，再使用500-1000d透析袋透析72h，冷冻干燥得到棕色荧光碳点粉末。
将30g聚碳酸酯二醇(Mn＝2000)加热到100℃，负压环境下脱水1h；再加入13.33g4,4'-二苯基甲烷二异氰酸酯(MDI)在80℃环境下搅拌反应3.5h，搅拌转速为400r/min；降温至50℃，加入1.39g的一缩二乙二醇进行扩链，升温至70℃，搅拌反应1h；降温至50℃，加入T9、T12催化剂与荧光碳点，升温至60-65℃，催化反应4h；整个反应过程中，使用丙酮进行黏度调节，反应结束至于PTFE板上，室温成膜。
将荧光聚氨酯膜溶于有机溶剂中，获得聚氨酯溶液，再将所述溶液通过静电纺丝机纺成膜，即可得荧光聚氨酯锂电池隔膜。
以正极片、负极片、电解液以及所制备的荧光聚氨酯锂电池隔膜为主要原料，组装锂电池。
实施例3
一种荧光聚氨酯锂电池隔膜，首先取2g柠檬酸、5g尿素溶与3g乙二胺于烧杯中，加入适量去离子水，烧杯用保鲜膜封口，于微波炉中高火微波5min，得到棕色溶液，再使用500-1000d透析袋透析72h，冷冻干燥得到棕色荧光碳点粉末。
将30g聚己二酸新戊二醇酯二元醇(Mn＝2000)加热到100℃，负压环境下脱水1h；再加入13.33g甲苯二异氰酸酯(TDI)在80℃环境下搅拌反应3.5h，搅拌转速为400r/min；降温至50℃，加入1.39g一缩二乙二醇进行扩链，升温至70℃，搅拌反应1h；降温至50℃，加入T9、T12催化剂与荧光碳点，升温至60-65℃，催化反应4h；整个反应过程中，使用丙酮进行黏度调节，反应结束至于PTFE板上，室温成膜。
将荧光聚氨酯膜溶于有机溶剂中，获得聚氨酯溶液，再将所述溶液通过静电纺丝机纺成膜，即可得荧光聚氨酯锂电池隔膜。
以正极片、负极片、电解液以及所制备的荧光聚氨酯锂电池隔膜为主要原料，组装锂电池。
以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然能够对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。

Claims (10)

1.一种荧光聚氨酯锂电池隔膜，其特征在于，所述荧光聚氨酯电池隔膜的原料包括多异氰酸酯、大分子多元醇、小分子多元醇和/或多元胺扩链剂、催化剂以及荧光碳点。
2.根据权利要求1所述荧光聚氨酯锂电池隔膜，其特征在于，所述荧光碳点的原料包括尿素、柠檬酸、乙二胺，其中，尿素质量分数为5％-30％，柠檬酸质量分数为35％-50％，乙二胺质量分数为20％-60％。
3.根据权利要求1或2所述荧光聚氨酯锂电池隔膜，其特征在于，所述荧光碳点的合成过程为：取不同质量比的柠檬酸、尿素溶于盛有乙二胺的烧杯中，加入适量去离子水，烧杯用保鲜膜封口，于微波炉中高火微波5min，得到棕色溶液，然后使用500-1000d透析袋透析72h，冷冻干燥得到棕色荧光碳点粉末。
4.根据权利要求1或2所述荧光聚氨酯锂电池隔膜，其特征在于，所述荧光聚氨酯的合成步骤为：
S1：将大分子多元醇加热到100℃，负压环境下脱水；
S2：向S1经脱水制得的大分子多元醇中加入多异氰酸酯，在75-95℃环境下搅拌反应3.5h，搅拌转速为400r/min；
S3：降温至50℃，加入扩链剂，升温至70-80℃，搅拌反应1h；
S4：再降温至50℃，加入催化剂与荧光碳点，升温至60-70℃，催化反应4h；
S5：将S4制得的树脂倒在聚四氟乙烯板上，室温成膜储存；
其中，整个反应过程中，使用有机溶剂进行黏度调节。
5.根据权利要求4所述荧光聚氨酯锂电池隔膜，其特征在于，所述多异氰酸酯为异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、甲苯二异氰酸酯(TDI)、4,4'-二苯基甲烷二异氰酸酯(MDI)、4,4'-二环己基甲烷二异氰酸酯(HMDI)中的一种或多种；所述大分子多元醇为聚酯二元醇、聚醚二元醇、聚醚聚酯二元醇中的一种或多种；所述小分子多元醇和/或多元胺扩链剂为1,4-丁二醇、一缩二乙二醇、乙二胺、水合肼中的一种或多种。
6.根据权利要求4所述荧光聚氨酯锂电池隔膜，其特征在于，所述有机溶剂为丙酮、乙酸乙酯、N,N-二甲基甲酰胺、N-甲基吡咯烷酮中的一种或多种。
7.根据权利要求4所述荧光聚氨酯锂电池隔膜，其特征在于，所述荧光碳点含量为体系总质量的1‰-5‰。
8.一种如权利要求1-7任一项所述荧光聚氨酯锂电池隔膜的制备方法，其特征在于，将荧光聚氨酯溶于有机溶剂中，得到聚氨酯溶液，再将所述溶液通过静电纺丝机纺成膜。
9.一种荧光聚氨酯锂电池隔膜，其特征在于，根据权利要求8所述的制备方法制得。
10.一种锂电池，其特征在于，使用权利要求9所述的荧光聚氨酯制备锂电池隔膜。
CN202211348144.7A 2022-10-31 2022-10-31 一种荧光聚氨酯锂电池隔膜及其制备方法、锂电池 Pending CN115632210A (zh)

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