CN108777320B - 一种含n、p原子互穿网络聚合物电解质的制备方法 - Google Patents

一种含n、p原子互穿网络聚合物电解质的制备方法 Download PDF

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CN108777320B
CN108777320B CN201810447216.0A CN201810447216A CN108777320B CN 108777320 B CN108777320 B CN 108777320B CN 201810447216 A CN201810447216 A CN 201810447216A CN 108777320 B CN108777320 B CN 108777320B
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麻金海
孔淑玲
方龙
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Abstract

本发明涉及一种以丙烯酸锂、顺丁烯二酸酐、次亚磷酸锂、烯丙基磺酸锂、聚乙二醇‑6000、乙醇胺和环氧氯丙烷为原料制备的互穿网络聚合物电解质的制备方法。本发明首先在水介质中将乙醇胺与环氧氯丙烷由氢氧化锂引发聚合，制备乙醇胺‑环氧氯丙烷树枝状聚合物水溶液，再以顺丁烯二酸酐和聚乙二醇为原料制备双‑顺丁烯二酸单聚乙二醇酯‑6000；然后将其与丙烯酸锂、次亚磷酸锂和烯丙基磺酸锂一起加入到乙醇胺‑环氧氯丙烷树枝状聚合物水溶液中，由双氧水和硫酸铁铵引发聚合，制备出含磷原子和氮原子的互穿网络聚合物电解质。

Description

一种含N、P原子互穿网络聚合物电解质的制备方法
技术领域
本发明属凝胶电解质领域，特别是涉及一种由丙烯酸锂、顺丁烯二酸酐、次亚磷酸锂、烯丙基磺酸锂、聚乙二醇-6000、乙醇胺和环氧氯丙烷为原料制备的互穿网络聚合物电解质及其制备方法。
背景技术
聚合物电解质的关键所在是将离子导电率提高至锂离子电池所要求的室温离子导电率的10-3S/cm的水平。其主要发展方向有单离子聚合物电解质、悬挂有聚醚链的网络聚合物电解质以及两相聚合物电解质等。但目前能够达到这一水平的聚合物电解质甚少，因此制备出符合锂离子电池导电率所要求的聚合物电解质意义非常重要。本发明综合锂离子聚合物电解质的三个发展方向，以丙烯酸锂、顺丁烯二酸酐、次亚磷酸锂、烯丙基磺酸锂、聚乙二醇-6000、乙醇胺和环氧氯丙烷为原料，在水介质中通过多步反应制备了含N、P原子的互穿网络聚合物，该聚合物电解质具有较高的强度、稳定性和离子导电率。
发明内容
本发明首先将乙醇胺与环氧氯丙烷在水介质中，由氢氧化锂引发聚合，制备乙醇胺-环氧氯丙烷树枝状聚合物水溶液，再以顺丁烯二酸酐和聚乙二醇为原料制备双-顺丁烯二酸单聚乙二醇酯-6000；然后将其与丙烯酸锂、次亚磷酸锂和烯丙基磺酸锂一起加入到乙醇胺-环氧氯丙烷树枝状聚合物水溶液中，由双氧水和硫酸铁铵引发聚合，制备出含磷原子和氮原子的互穿网络聚合物电解质。
具体实施方式
实施例1
(1)乙醇胺-环氧氯丙烷树枝状聚合物的制备
于三口反应瓶中，加入0.050mol乙醇胺，0.050mol氢氧化锂和20ml蒸馏水，25℃下搅拌溶解，升温至90℃，缓慢滴加0.200mol环氧氯丙烷，加完后，继续保温反应6h，冷却至室温，得黄色粘稠液体；
(2)双-顺丁烯二酸单聚乙二醇酯的制备
将0.050mol顺丁烯二酸酐，0.025mol聚乙二醇-6000和1.000g对甲苯磺酸置于100ml带有冷凝管和分水器的三口反应瓶中，加热至105℃熔融，搅拌反应5h，分出水分，趁热倒入烧杯中，冷却至室温，得蜡状固体；
(3)互穿网络聚合物的制备
分别将上述(1)和(2)中制备的样品加入100ml蒸馏水中，搅拌溶解，再依次加入0.050mol丙烯酸锂，0.100mol烯丙基磺酸锂和0.020mol次亚磷酸锂，搅拌溶解，通氮气10分钟，然后加入0.002g硫酸铁铵，搅拌溶解，升温至75℃，缓慢加入5.00g质量浓度为30％双氧水，引发聚合，需要5h，逐渐析出淡黄色粘性凝胶，冷却至室温，倒出上部清液，刮出凝胶，无水乙醇洗涤3次，25℃自然干燥，得黄色凝胶。
实施例2
(1)聚合物凝胶强度
取实施例1(3)的样品，于不同温度下，调节流变仪剪切速率为500S-1，测定凝胶的强度。见表1。
表1 聚合物凝胶的抗剪切强度(剪切速率：500S-1)
温度，℃ -20 -10 0 10 20 50 80
抗剪切强度，Pa 25.54 24.39 23.1 20.36 17.42 15.31 8.22
(2)聚合物吸水率
准确取实施例1(3)的样品分别置于5％的氯化锂水溶液中，然后将其密封于一定温度下浸泡一定时间，擦去表面水分，测定不同时间聚合物的吸水率。见表2。
表2 聚合物的吸水率
Figure GSB0000190140160000021
(3)聚合物成型收缩率
将实施例1(3)的样品加热至100℃，使用带百分表的模具(精度为0.01mm)制成尺寸为25.000mmx、10.000mmx和3.000mm的长条，分别测定长条试样出模后冷却至50℃、40℃、30℃、20℃、10℃和0℃在平行于流动方向上的尺寸变化。计算试样的成型收缩率(S)。见表3。
表3 聚合物成型收缩率
出模后冷却温度，℃ 0 10 20 30 40 50
成型收缩率，％ 0.62 0.62 0.60 0.56 0.52 0.37
(4)聚合物失重率
将一定量的实施例1(3)的样品置于称量瓶中。然后将其密封于高压罐中，老化箱内一定温度下保温老化一定时间，冷却、开启密封罐、取出称量瓶，称重。测定凝胶样品在不同温度、不同老化时间的失重率。结果见表4。
表4 不同老化温度下的失重率
Figure GSB0000190140160000031
由表4可以看出，温度小于100℃，聚合物失重小于1.0％；当温度大于100℃时，随着温度的升高以及老化时间的延长，失重率增大。150℃，老化时间10d，失重率为1.15％；随着时间延长，失重率保持恒定。
实施例3
在体系冷却前，将一定尺寸的实施例1(3)的聚合物电解质膜夹在两片金属电极间，连接好测量线路。测定出电极面积A与聚合物电解质膜的厚度d。设定扫描频率范围从1Hz到105Hz，用Solartron SI1287+SI1260型电化学综合测试仪测定样品在温度为-20℃～25℃下的交流阻抗谱。由交流阻抗图谱中尾线与实轴的交点，读取凝胶样品的电阻Rb，按公式：σ＝d/(Rb·A)计算该聚合物电解质的电导率。见表5
表5 不同温度下凝胶离子导电率
温度，℃ -20 -10 0 10 25
离子导电率，S/cm 5.50×10<sup>-6</sup> 7.09×10<sup>-5</sup> 1.21×10<sup>-4</sup> 8.08×10<sup>-4</sup> 7.52×10<sup>-3</sup>

Claims (1)

1.一种以丙烯酸锂、顺丁烯二酸酐、次亚磷酸锂、烯丙基磺酸锂、聚乙二醇-6000、乙醇胺和环氧氯丙烷为原料制备的互穿网络聚合物电解质的制备方法，包括下列步骤：
(1)乙醇胺-环氧氯丙烷树枝状聚合物的制备
于三口反应瓶中，加入0.050mol乙醇胺，0.050mol氢氧化锂和20ml蒸馏水，25℃下搅拌溶解，升温至90℃，缓慢滴加0.200mol环氧氯丙烷，加完后，继续保温反应6h，冷却至室温，得黄色粘稠液体；
(2)双-顺丁烯二酸单聚乙二醇酯的制备
将0.050mol顺丁烯二酸酐，0.025mol聚乙二醇-6000和1.000g对甲苯磺酸置于100ml带有冷凝管和分水器的三口反应瓶中，加热至105℃熔融，搅拌反应5h，分出水分，趁热倒入烧杯中，冷却至室温，得蜡状固体；
(3)互穿网络聚合物的制备
分别将上述(1)和(2)中制备的样品加入100ml蒸馏水中，搅拌溶解，再依次加入0.050mol丙烯酸锂，0.100mol烯丙基磺酸锂和0.020mol次亚磷酸锂，搅拌溶解，通氮气10分钟，然后加入0.002g硫酸铁铵，搅拌溶解，升温至75℃，缓慢加入5.00g质量浓度为30％的双氧水，引发聚合，需要5h，逐渐析出淡黄色粘性凝胶，冷却至室温，倒出上部清液，刮出凝胶，无水乙醇洗涤3次，25℃自然干燥，得黄色凝胶。
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