CN113235300A - 一种耐高温的锂离子电池复合隔膜的制备方法 - Google Patents
一种耐高温的锂离子电池复合隔膜的制备方法 Download PDFInfo
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Abstract
本发明公开了一种耐高温的锂离子电池复合隔膜的制备方法，包括将苯乙烯‑丁二烯‑苯乙烯嵌段共聚物加入到四氢呋喃和N,N‑二甲基甲酰胺混合溶剂中，加热至50～55℃搅拌溶解，得到A液；将聚丙烯腈加入到N,N‑二甲基甲酰胺中，加热至45～50℃搅拌溶解，得到B液，然后将A液和B液分别移至注射泵中，采用对喷的方式，在接收辊上得到纤维膜；将步骤S1中得到的纤维膜放置在蒸馏水中，然后加入酒石酸，加热至90～95℃摇荡3～5h，将捞出该纤维膜，重新放置在蒸馏水中，加入氧化镍，再次加热至60～70℃进行摇荡2～3h，得到改性纤维膜I；将步骤S2得到的改性纤维膜I加入到多巴胺水溶液中，移至高压反应釜中，在100～120℃下反应1.5～3h后冷却，捞出纤维膜在真空环境下进行干燥，得到所述复合隔膜。
Description
技术领域
本发明属于锂离子电池隔膜技术领域，具体涉及一种耐高温的锂离子电池复合隔膜的制备方法。
背景技术
锂离子电池由于具有高比能量、长循环寿命和环境友好等优点，广泛应用于便携电子产品、电动汽车等领域。新一代便携电子产品和电动汽车的发展对锂离子电池的安全性和能量密度提出了更高的要求。隔膜是锂离子电池的重要组件之一，其作用是防止正负极间的物理接触，并通过吸收电解液提供离子传导能力。虽然隔膜并不直接参与电池反应，但它的结构和性质决定了电池的性能，包括循环性、安全性、能量和功率密度等。目前商品化的锂离子电池隔膜主要采用聚烯烃多孔膜，如为聚乙烯(PE)、聚丙烯(PP)以及它们的复合隔膜，虽然它们具有良好的化学稳定性及优良的机械性能，但是其较差的电解液亲和性以及热稳定性限制了其在新一代锂离子电池中的应用。为了抑制隔膜在高温下的形变，通常采用在隔膜基底上涂覆无机氧化物的方法来提高隔膜的热稳定性，如专利CN105449141A中采用无机粒子和有机粒子共混涂膜聚烯烃膜，但是此类隔膜在过高温度下，仍然允许电池内部锂离子通过，造成电池内部温度继续升高，最终发生燃烧甚至爆炸。
发明内容
本发明的目的是提供一种耐高温的锂离子电池复合隔膜的制备方法，所述制备方法包括以下步骤：
S1：将苯乙烯-丁二烯-苯乙烯嵌段共聚物加入到四氢呋喃和N,N-二甲基甲酰胺混合溶剂中，加热至50～55℃搅拌溶解，得到A液；将聚丙烯腈加入到N,N-二甲基甲酰胺中，加热至45～50℃搅拌溶解，得到B液，然后将A液和B液分别移至注射泵中，采用对喷的方式，在接收辊上得到纤维膜。
S2：将步骤S1中得到的纤维膜放置在蒸馏水中，然后加入酒石酸，加热至90～95℃摇荡3～5h，然后将捞出该纤维膜，重新放置在蒸馏水中，加入氧化镍，再次加热至60～70℃进行摇荡2～3h，得到改性纤维膜I。
S3：将步骤S2得到的改性纤维膜I加入到多巴胺水溶液中，然后移至高压反应釜中，在100～120℃下反应1.5～3h后冷却，捞出纤维膜在真空环境下进行干燥，得到所述复合隔膜。
作为优选方案，上述所述的四氢呋喃和N,N-二甲基甲酰胺混合溶剂中四氢呋喃和N,N-二甲基甲酰胺的体积比为1:1～2。
作为优选方案，上述所述的苯乙烯-丁二烯-苯乙烯嵌段共聚物和混合溶剂的质量体积比为(1.2～1.4)g:(11～15)mL；所述聚丙烯腈和N,N-二甲基甲酰胺的质量体积比为(1.1～1.4)g:(10～16)mL。
作为优选方案，上述所述A液静电纺丝的注射电压为20～26kV，注射速率为0.45～0.5mL/h，注射距离为12～16cm；所述B液电纺丝的注射电压为15～20kV，注射速率为0.40～0.45mL/h，注射距离为8～12cm。
作为优选方案，上述所述的酒石酸和蒸馏水的质量体积比为(2.3～2.8)g:(20～30)mL；所述氧化镍和蒸馏水的质量体积比为(0.96～1.26)g:(16～25)mL。
作为优选方案，上述所述的多巴胺水溶液的质量百分浓度为25～36％。
与现有技术相比，本发明具有如下有益效果：
本发明中，采用苯乙烯-丁二烯-苯乙烯嵌段共聚物和聚丙烯腈进行混合静电纺丝，然后使用酒石酸进行改性在负载氧化镍，最后使用多巴胺，利用多巴胺的成膜性对负载物进行包覆，得到的隔膜具有良好的吸液效果、拉伸效果和孔隙率，好具有优异的离子导电率。
附图说明
图1为本发明实施例1制备复合隔膜的SEM图谱。
具体实施方式
下面对本发明实施例作具体详细的说明，本实施例在本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
实施例1
一种耐高温的锂离子电池复合隔膜的制备方法，具体包括以下步骤：
S1：将苯乙烯-丁二烯-苯乙烯嵌段共聚物加入到体积比为1:1～2的四氢呋喃和N,N-二甲基甲酰胺混合溶剂中，加热至50～55℃搅拌溶解，得到A液；将聚丙烯腈加入到N,N-二甲基甲酰胺中，加热至45～50℃搅拌溶解，得到B液，然后将A液和B液分别移至注射泵中，采用对喷的方式，在接收辊上得到纤维膜，其中苯乙烯-丁二烯-苯乙烯嵌段共聚物和混合溶剂的质量体积比为(1.2～1.4)g:(11～15)mL；所述聚丙烯腈和N,N-二甲基甲酰胺的质量体积比为(1.1～1.4)g:(10～16)mL；A液静电纺丝的注射电压为20～26kV，注射速率为0.45～0.5mL/h，注射距离为12～16cm；所述B液电纺丝的注射电压为15～20kV，注射速率为0.40～0.45mL/h，注射距离为8～12cm。
S2：将步骤S1中得到的纤维膜放置在蒸馏水中，然后加入酒石酸，加热至90～95℃摇荡3～5h，然后将捞出该纤维膜，重新放置在蒸馏水中，加入氧化镍，再次加热至60～70℃进行摇荡2～3h，得到改性纤维膜I，其中酒石酸和蒸馏水的质量体积比为(2.3～2.8)g:(20～30)mL；所述氧化镍和蒸馏水的质量体积比为(0.96～1.26)g:(16～25)mL。
S3：将步骤S2得到的改性纤维膜I加入到多巴胺水溶液中，然后移至高压反应釜中，在100～120℃下反应1.5～3h后冷却，捞出纤维膜在真空环境下进行干燥，得到所述复合隔膜，其中多巴胺水溶液的质量百分浓度为25～36％。
实施例2
一种耐高温的锂离子电池复合隔膜的制备方法，具体包括以下步骤：
S1：将苯乙烯-丁二烯-苯乙烯嵌段共聚物加入到体积比为1:1～2的四氢呋喃和N,N-二甲基甲酰胺混合溶剂中，加热至50～55℃搅拌溶解，得到A液；将聚丙烯腈加入到N,N-二甲基甲酰胺中，加热至45～50℃搅拌溶解，得到B液，然后将A液和B液分别移至注射泵中，采用对喷的方式，在接收辊上得到纤维膜，其中苯乙烯-丁二烯-苯乙烯嵌段共聚物和混合溶剂的质量体积比为(1.2～1.4)g:(11～15)mL；所述聚丙烯腈和N,N-二甲基甲酰胺的质量体积比为(1.1～1.4)g:(10～16)mL；A液静电纺丝的注射电压为20～26kV，注射速率为0.45～0.5mL/h，注射距离为12～16cm；所述B液电纺丝的注射电压为15～20kV，注射速率为0.40～0.45mL/h，注射距离为8～12cm。
S2：将步骤S1中得到的纤维膜放置在蒸馏水中，然后加入酒石酸，加热至90～95℃摇荡3～5h，然后将捞出该纤维膜，重新放置在蒸馏水中，加入氧化镍，再次加热至60～70℃进行摇荡2～3h，得到改性纤维膜I，其中酒石酸和蒸馏水的质量体积比为(2.3～2.8)g:(20～30)mL；所述氧化镍和蒸馏水的质量体积比为(0.96～1.26)g:(16～25)mL。
S3：将步骤S2得到的改性纤维膜I加入到多巴胺水溶液中，然后移至高压反应釜中，在100～120℃下反应1.5～3h后冷却，捞出纤维膜在真空环境下进行干燥，得到所述复合隔膜，其中多巴胺水溶液的质量百分浓度为25～36％。
实施例3
一种耐高温的锂离子电池复合隔膜的制备方法，具体包括以下步骤：
S1：将苯乙烯-丁二烯-苯乙烯嵌段共聚物加入到体积比为1:1～2的四氢呋喃和N,N-二甲基甲酰胺混合溶剂中，加热至50～55℃搅拌溶解，得到A液；将聚丙烯腈加入到N,N-二甲基甲酰胺中，加热至45～50℃搅拌溶解，得到B液，然后将A液和B液分别移至注射泵中，采用对喷的方式，在接收辊上得到纤维膜，其中苯乙烯-丁二烯-苯乙烯嵌段共聚物和混合溶剂的质量体积比为(1.2～1.4)g:(11～15)mL；所述聚丙烯腈和N,N-二甲基甲酰胺的质量体积比为(1.1～1.4)g:(10～16)mL；A液静电纺丝的注射电压为20～26kV，注射速率为0.45～0.5mL/h，注射距离为12～16cm；所述B液电纺丝的注射电压为15～20kV，注射速率为0.40～0.45mL/h，注射距离为8～12cm。
S2：将步骤S1中得到的纤维膜放置在蒸馏水中，然后加入酒石酸，加热至90～95℃摇荡3～5h，然后将捞出该纤维膜，重新放置在蒸馏水中，加入氧化镍，再次加热至60～70℃进行摇荡2～3h，得到改性纤维膜I，其中酒石酸和蒸馏水的质量体积比为(2.3～2.8)g:(20～30)mL；所述氧化镍和蒸馏水的质量体积比为(0.96～1.26)g:(16～25)mL。
S3：将步骤S2得到的改性纤维膜I加入到多巴胺水溶液中，然后移至高压反应釜中，在100～120℃下反应1.5～3h后冷却，捞出纤维膜在真空环境下进行干燥，得到所述复合隔膜，其中多巴胺水溶液的质量百分浓度为25～36％。
实施例4
一种耐高温的锂离子电池复合隔膜的制备方法，具体包括以下步骤：
S1：将苯乙烯-丁二烯-苯乙烯嵌段共聚物加入到体积比为1:1～2的四氢呋喃和N,N-二甲基甲酰胺混合溶剂中，加热至50～55℃搅拌溶解，得到A液；将聚丙烯腈加入到N,N-二甲基甲酰胺中，加热至45～50℃搅拌溶解，得到B液，然后将A液和B液分别移至注射泵中，采用对喷的方式，在接收辊上得到纤维膜，其中苯乙烯-丁二烯-苯乙烯嵌段共聚物和混合溶剂的质量体积比为(1.2～1.4)g:(11～15)mL；所述聚丙烯腈和N,N-二甲基甲酰胺的质量体积比为(1.1～1.4)g:(10～16)mL；A液静电纺丝的注射电压为20～26kV，注射速率为0.45～0.5mL/h，注射距离为12～16cm；所述B液电纺丝的注射电压为15～20kV，注射速率为0.40～0.45mL/h，注射距离为8～12cm。
S2：将步骤S1中得到的纤维膜放置在蒸馏水中，然后加入酒石酸，加热至90～95℃摇荡3～5h，然后将捞出该纤维膜，重新放置在蒸馏水中，加入氧化镍，再次加热至60～70℃进行摇荡2～3h，得到改性纤维膜I，其中酒石酸和蒸馏水的质量体积比为(2.3～2.8)g:(20～30)mL；所述氧化镍和蒸馏水的质量体积比为(0.96～1.26)g:(16～25)mL。
S3：将步骤S2得到的改性纤维膜I加入到多巴胺水溶液中，然后移至高压反应釜中，在100～120℃下反应1.5～3h后冷却，捞出纤维膜在真空环境下进行干燥，得到所述复合隔膜，其中多巴胺水溶液的质量百分浓度为25～36％。
性能测试：(1)将实施例1～4制备的隔膜裁剪成半径为8cm的样品，分别在200℃真空干燥箱中处理2h，并比较热处理前后隔膜形态的变化；(2)将实施例1～4制备的隔膜热压后的纤维膜截取成大小相同的尺寸，称其质量为W0，然后将其放入装有正丁醇的密闭容器中浸泡6h，取出样品，并用滤纸将其表面残留的正丁醇擦拭干净，称其质量为W1，采用下式计算：
W0为浸泡前隔膜的质量(g)；W1为浸泡后隔膜的质量(g)；VP为浸泡前隔膜的体积(cm3)；ρp为正丁醇密度(g/cm3)；(3)将实施例1～4制备的隔膜截取面积相同的隔膜置于干燥箱中干燥完成后，称其质量为W0，然后置于装有电解液的密闭容器中浸泡6h，取出样品用滤纸擦干表面液体，称其质量为W1，采用下式计算：
(4)将实施例1～4制备的隔膜裁成大小相同的长方形条状，采用拉伸力学试验机对隔膜样品进行拉伸试验，每组5个样品，在相同的速率下测试；(5)对实施例1～4制备的隔膜进行离子电导率测试，测试结果如表1所示，
表1.测试结果：
从表1中可以看出，实施例1～4中的复合隔膜在240℃下加热处理2h后，其隔膜的形态结构依然保持良好，说明本发明隔膜具有良好的热稳定性；并且其孔隙率均在50.5％，吸液率保持在322.6％以上，具有良好的吸液效果，拉伸强度在21.67MPa以上，电导率均在4.16×10-4以上，说明本发明隔膜具有良好综合性能。
Claims (6)
1.一种耐高温的锂离子电池复合隔膜的制备方法，其特征在于，所述制备方法包括以下步骤：
S1：将苯乙烯-丁二烯-苯乙烯嵌段共聚物加入到四氢呋喃和N,N-二甲基甲酰胺混合溶剂中，加热至50～55℃搅拌溶解，得到A液；将聚丙烯腈加入到N,N-二甲基甲酰胺中，加热至45～50℃搅拌溶解，得到B液，然后将A液和B液分别移至注射泵中，采用对喷的方式，在接收辊上得到纤维膜；
S2：将步骤S1中得到的纤维膜放置在蒸馏水中，然后加入酒石酸，加热至90～95℃摇荡3～5h，然后将捞出该纤维膜，重新放置在蒸馏水中，加入氧化镍，再次加热至60～70℃进行摇荡2～3h，得到改性纤维膜I；
S3：将步骤S2得到的改性纤维膜I加入到多巴胺水溶液中，然后移至高压反应釜中，在100～120℃下反应1.5～3h后冷却，捞出纤维膜在真空环境下进行干燥，得到所述复合隔膜。
2.根据权利要求1所述的一种耐高温的锂离子电池复合隔膜的制备方法，其特征在于，所述的四氢呋喃和N,N-二甲基甲酰胺混合溶剂中四氢呋喃和N,N-二甲基甲酰胺的体积比为1:1～2。
3.根据权利要求1所述的一种耐高温的锂离子电池复合隔膜的制备方法，其特征在于，所述的苯乙烯-丁二烯-苯乙烯嵌段共聚物和混合溶剂的质量体积比为(1.2～1.4)g:(11～15)mL；所述聚丙烯腈和N,N-二甲基甲酰胺的质量体积比为(1.1～1.4)g:(10～16)mL。
4.根据权利要求1所述的一种耐高温的锂离子电池复合隔膜的制备方法，其特征在于，所述A液静电纺丝的注射电压为20～26kV，注射速率为0.45～0.5mL/h，注射距离为12～16cm；所述B液电纺丝的注射电压为15～20kV，注射速率为0.40～0.45mL/h，注射距离为8～12cm。
5.根据权利要求1所述的一种耐高温的锂离子电池复合隔膜的制备方法，其特征在于，所述的酒石酸和蒸馏水的质量体积比为(2.3～2.8)g:(20～30)mL；所述氧化镍和蒸馏水的质量体积比为(0.96～1.26)g:(16～25)mL。
6.根据权利要求1所述的一种耐高温的锂离子电池复合隔膜的制备方法，其特征在于，所述的多巴胺水溶液的质量百分浓度为25～36％。
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