CN114213789B - 一种硼酸酯聚合物/离子液体复合导电凝胶及其制备方法和应用 - Google Patents
一种硼酸酯聚合物/离子液体复合导电凝胶及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种硼酸酯聚合物/离子液体复合导电凝胶及其制备方法和应用，由混合溶剂、乙烯‑乙烯醇共聚物、离子液体、硼酸和含双邻苯二酚基团化合物制成。本发明具有自修复、宽温度适用范围、导电性的功能，特别使用于超级电容器和电池等领域并拓宽其温度使用范围(‑20℃‑120℃)和延长寿命(在受损伤不严重的情况下，可以自我修复)。
Description
技术领域
本发明属于功能高分子技术领域，具体涉及一种硼酸酯聚合物/离子液体复合导电凝胶及其制备方法和应用。
背景技术
有机凝胶是以有机溶剂作为介质，由高分子或聚合物交联形成的软物质材料。有机凝胶不仅拥有水凝胶的柔软性、优异的机械性能等优点，还具有其独特的性质如：亲/疏水性、耐热性和防冻性等，这些性质均能通过调节有机溶剂的种类和比例来实现。因此，有机凝胶被广泛运用在药物输送(尤其疏水性药物)、食品加工、耐热防冻、健康检测器、固态电解质和超级电容器等方面。具有宽温度适用范围的有机凝胶能摆脱一般有机凝胶高温下严重脱水，低温下冻结的限制，因此宽温度适用范围的有机凝胶可以在极端的环境中仍保存有机凝胶的所有性能，使其有望运用在深空和海底探测等领域。
近年来，有报道使用高沸点有机溶剂如：DMSO(二甲基亚砜)、甘油(丙三醇)和乙二醇来制备有机凝胶，其使用的温度范围比一般有机凝胶要更宽。Zhang等人[HaoxiangZhang，WenbinNiu，and Shufen Zhang.Extremely Stretchable and Self-HealableElectrical Skin with Mechanical Adaptability，an Ultrawide Linear ResponseRange，and Excellent Temperature Tolerance.ACS Appl.Mater.Interfaces.2019]将聚乙烯吡咯烷酮(PVP)包封银纳米线引入聚丙烯酰胺和PVP的双网络中，乙二醇作为溶剂，使得有机凝胶具有防冻抗热(-20至80℃)和导电性。Li等人[Lefan Li，Qiao Wang，XiaoxuLiang，et al.Regulation of the elasticity and temperature tolerance ofpolyacrylamide/Ca(OH)2 nanocomposite organogel using a two-component organicsolvent.Polymer Testing.2021]将氢氧化钙(Ca(OH)2)纳米球粒加入丙烯酰胺溶液中原位聚合后，浸泡在双组份有机溶剂体系(乙二醇和丙三醇)中并真空干燥出水得到纳米复合有机凝胶，其温度适用范围为-25-110℃。然而，将有机凝胶作为固态电解质却鲜有报道，其主要原因是现有的有机凝胶的抗压性能、适应温度的变化和导电性能等一系列性能还未能达到使用要求，亟待改进。如果其抗压性能差和温度范围窄，在使用过程中会造成有机凝胶的变形，甚至破裂进而导致安全事故，这些都会限制其在实际环境中的使用。
发明内容
本发明的目的在于克服现有技术缺陷，提供一种硼酸酯聚合物/离子液体复合导电凝胶。
本发明的另一目的在于提供上述硼酸酯聚合物/离子液体复合导电凝胶的制备方法。
本发明的再一目的在于提供上述硼酸酯聚合物/离子液体复合导电凝胶的应用。
本发明的而技术方案如下：
一种硼酸酯聚合物/离子液体复合导电凝胶，其特征在于：由混合溶剂、乙烯-乙烯醇共聚物、离子液体、硼酸和含双邻苯二酚基团化合物制成，其中，
混合溶剂由DMSO和异丙醇以5-8∶2-5的体积比混合而成，
乙烯-乙烯醇共聚物中乙烯的含量为30-34wt％，
含双邻苯二酚基团化合物为单宁酸、鞣花酸、6，6′，7，7′-四羟基-4，4，4′，4′-四甲基-2，2′-螺双苯并二氢吡喃、绿原酸或芸香苷水合物，
离子液体为四丁基四氟硼酸铵、1-己基-3-甲基咪唑三氟甲磺酸盐、1-乙基-3-甲基咪唑双三氟甲基磺酰亚胺、1-正丁基-3-甲基咪唑六氟磷酸盐、1-乙基-3-甲基咪唑四氟硼酸盐和1-丁基-2，3-二甲基咪唑六氟磷酸盐中的至少一种。
在本发明的一个优选实施方案中，所述含双邻苯二酚基团化合物为单宁酸。
在本发明的一个优选实施方案中，所述离子液体为四丁基四氟硼酸铵、1-己基-3-甲基咪唑三氟甲磺酸盐、1-乙基-3-甲基咪唑双三氟甲基磺酰亚胺、1-正丁基-3-甲基咪唑六氟磷酸盐、1-乙基-3-甲基咪唑四氟硼酸盐或1-丁基-2，3-二甲基咪唑六氟磷酸盐。
在本发明的一个优选实施方案中，所述混合溶剂由DMSO和异丙醇以8∶2的体积比混合而成。
在本发明的一个优选实施方案中，所述含双邻苯二酚基团化合物为单宁酸，所述离子液体为四丁基四氟硼酸铵、1-己基-3-甲基咪唑三氟甲磺酸盐、1-乙基-3-甲基咪唑双三氟甲基磺酰亚胺、1-正丁基-3-甲基咪唑六氟磷酸盐、1-乙基-3-甲基咪唑四氟硼酸盐或1-丁基-2，3-二甲基咪唑六氟磷酸盐，所述混合溶剂由DMSO和异丙醇以8∶2的体积比混合而成。
进一步优选的，由混合溶剂、乙烯-乙烯醇共聚物、离子液体、硼酸和含双邻苯二酚基团化合物以10-11∶2-3∶0.1-1∶0.372∶0.34的质量比制成。
上述硼酸酯聚合物/离子液体复合导电凝胶的制备方法，包括如下步骤：
(1)将所述乙烯-乙烯醇共聚物与所述混合溶剂中的一部分于80-100℃下搅拌混合1-5h，获得EVOH溶液；
(2)将所述含双邻苯二酚基团化合物、离子液体、硼酸以及混合溶剂的另一部分于室温下搅拌混合1-3h，获得交联剂溶液；
(3)将步骤(1)所得的EVOH溶液和步骤(2)所得的交联剂溶液混合均匀，冷却至室温下即得所述硼酸酯聚合物/离子液体复合导电凝胶。
在本发明的一个优选实施方案中，所述EVOH溶液的浓度为20-30wt％。
在本发明的一个优选实施方案中，所述步骤(1)为：将所述乙烯-乙烯醇共聚物与所述混合溶剂中的一部分于95℃下搅拌混合3h，获得EVOH溶液。
上述硼酸酯聚合物/离子液体复合导电凝胶作为固态电解质的应用。
本发明的有益效果是：
1、本发明的基本骨架为乙烯-乙烯醇共聚物网络，其中引入硼酸形成了可逆硼酸酯键，在有机凝胶内部形成交联点，并具有良好的机械性能和自修复性能。
2、本发明采用特定的高沸点的混合有机溶剂制备，具有宽温度适用范围。
3、本发明引入离子液体，增加了有机凝胶内部的离子迁移，使其具有良好的导电性。
4、本发明的有机凝胶兼具有自修复、宽温度适用范围、导电性的功能，特别使用于超级电容器和电池等领域并拓宽其温度使用范围(-20℃-120℃)和延长寿命(在受损伤不严重的情况下，可以自我修复)。
附图说明
图1为本发明实施例1至3制得的硼酸酯聚合物/离子液体复合导电凝胶的流变温度扫描谱对比图。
图2为本发明实施例4至9制得的硼酸酯聚合物/离子液体复合导电凝胶的流变温度扫描谱对比图。
图3为本发明实施例1至3制得的硼酸酯聚合物/离子液体复合导电凝胶的压缩对比图。
图4为本发明实施例4至9制得的硼酸酯聚合物/离子液体复合导电凝胶的压缩对比图。
图5为本发明实施例1至3制得的硼酸酯聚合物/离子液体复合导电凝胶的交流阻抗对比图。
图6为本发明实施例4至9制得的硼酸酯聚合物/离子液体复合导电凝胶的交流阻抗对比图。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
实施例1
(1)将2g EVOH溶于8g混合溶剂(DMSO和异丙醇的体积比为8∶2)中，在95℃下搅拌3h，得到20wt％EVOH溶液。
(2)将0.34g单宁酸、0.1g四丁基四氟硼酸铵、0.372g硼酸溶于3g混合溶剂中，在室温下搅拌1h，得到交联剂溶液。
(3)将(2)所得交联剂溶液与(1)所得EVOH溶液混合，冷却至室温后得到如图1、3和5所示的硼酸酯聚合物/离子液体复合导电凝胶，其凝胶点为87℃，电导率为0.181mS/cm。
实施例2
(1)将2.5g EVOH溶于7.5g混合溶剂(DMSO和异丙醇的体积比为8∶2)中，在95℃下搅拌3h，得到25wt％EVOH溶液。
(2)将0.34g单宁酸、0.1g四丁基四氟硼酸铵、0.372g硼酸溶于3g混合溶剂中，在室温下搅拌1h，得到交联剂溶液。
(3)将(2)所得交联剂溶液与(1)所得EVOH溶液混合，冷却至室温后得到如图1、3和5所示的硼酸酯聚合物/离子液体复合导电凝胶，其凝胶点为109℃，电导率为0.137mS/cm。
实施例3
(1)将3g EVOH溶于7g混合溶剂(DMSO和异丙醇的体积比为8∶2)中，在95℃下搅拌3h，得到30wt％EVOH溶液。
(2)将0.34g单宁酸、0.1g四丁基四氟硼酸铵、0.372g硼酸溶于3g混合溶剂中，在室温下搅拌1h，得到交联剂溶液。
(3)将(2)所得交联剂溶液与(1)所得EVOH溶液混合，冷却至室温后得到如图1、3和5所示的硼酸酯聚合物/离子液体复合导电凝胶，其凝胶点为120℃，电导率为0.171mS/cm。
实施例4
(1)将2g EVOH溶于8g溶液(DMSO和异丙醇的体积比为8∶2)中，在95℃下搅拌3h，得到20wt％EVOH溶液。
(2)将0.34g单宁酸、0.4g四丁基四氟硼酸铵、0.372g硼酸溶于3g混合溶剂中，在室温下搅拌1h，得到交联剂溶液。
(3)将(2)所得交联剂溶液与(1)所得EVOH溶液混合，冷却至室温后得到如图2、4和6所示的硼酸酯聚合物/离子液体复合导电凝胶，其凝胶点为110℃，电导率为1.570mS/cm。
实施例5
(1)将2g EVOH溶于8g混合溶剂(DMSO和异丙醇的体积比为8∶2)中，在95℃下搅拌3h，得到20wt％EVOH溶液。
(2)将0.34g单宁酸、0.4g 1-己基-3-甲基咪唑三氟甲磺酸盐、0.372g硼酸溶于3g混合溶剂中，在室温下搅拌1h，得到交联剂溶液。
(3)将(2)所得交联剂溶液与(1)所得EVOH溶液混合，冷却至室温后得到如图2、4和6所示的硼酸酯聚合物/离子液体复合导电凝胶，其凝胶点为154℃，电导率为1.153mS/cm。
实施例6
(1)将2g EVOH溶于8g混合溶剂(DMSO和异丙醇的体积比为8∶2)中，在95℃下搅拌3h，得到20wt％EVOH溶液。
(2)将0.34g单宁酸、0.4g 1-乙基-3-甲基咪唑双三氟甲基磺酰亚胺、0.372g硼酸溶于3g混合溶剂中，在室温下搅拌1h，得到交联剂溶液。
(3)将(2)所得交联剂溶液与(1)所得EVOH溶液混合，冷却至室温后得到如图2、4和6所示的硼酸酯聚合物/离子液体复合导电凝胶，其凝胶点为131℃，电导率为1.273mS/cm。
实施例7
(1)将2g EVOH溶于8g混合溶剂(DMSO和异丙醇的体积比为8∶2)中，在95℃下搅拌3h，得到20wt％EVOH溶液。
(2)将0.34g单宁酸、0.4g 1-正丁基-3-甲基咪唑六氟磷酸盐、0.372g硼酸溶于3g混合溶剂中，在室温下搅拌1h，得到交联剂溶液。
(3)将(2)所得交联剂溶液与(1)所得EVOH溶液混合，冷却至室温后得到如图2、4和6所示的硼酸酯聚合物/离子液体复合导电凝胶，其凝胶点为156℃，电导率为1.121mS/cm。
实施例8
(1)将2g EVOH溶于8g混合溶剂(DMSO和异丙醇的体积比为8∶2)中，在95℃下搅拌3h，得到20wt％EVOH溶液。
(2)将0.34g单宁酸、0.4g 1-乙基-3-甲基咪唑四氟硼酸盐、0.372g硼酸溶于3g混合溶剂中，在室温下搅拌1h，得到交联剂溶液。
(3)将(2)所得交联剂溶液与(1)所得EVOH溶液混合，冷却至室温后得到如图2、4和6所示的硼酸酯聚合物/离子液体复合导电凝胶，其凝胶点为93℃，电导率为1.555mS/cm。
实施例9
(1)将2g EVOH溶于8g混合溶剂(DMSO和异丙醇的体积比为8∶2)中，在95℃下搅拌3h，得到20wt％EVOH溶液。
(2)将0.34g单宁酸、0.4g 1-丁基-2，3-二甲基咪唑六氟磷酸盐、0.372g硼酸溶于3g混合溶剂中，在室温下搅拌1h，得到交联剂溶液。
(3)将(2)所得交联剂溶液与(1)所得EVOH溶液混合，冷却至室温后得到如图2、4和6所示的硼酸酯聚合物/离子液体复合导电凝胶，其凝胶点为137℃，电导率为1.220mS/cm。
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。
Claims (7)
1.一种硼酸酯聚合物/离子液体复合导电凝胶，其特征在于：由混合溶剂、乙烯-乙烯醇共聚物、离子液体、硼酸和单宁酸以10-11:2-3:0.1-1:0.372:0.34的质量比制成，其中，
混合溶剂由DMSO和异丙醇以5-8:2-5的体积比混合而成，
乙烯-乙烯醇共聚物中乙烯的含量为30-34wt%，
离子液体为四丁基四氟硼酸铵、1-己基-3-甲基咪唑三氟甲磺酸盐、1-乙基-3-甲基咪唑双三氟甲基磺酰亚胺、1-正丁基-3-甲基咪唑六氟磷酸盐、1-乙基-3-甲基咪唑四氟硼酸盐和1-丁基-2,3-二甲基咪唑六氟磷酸盐中的至少一种。
2.如权利要求1所述的硼酸酯聚合物/离子液体复合导电凝胶，其特征在于：所述离子液体为四丁基四氟硼酸铵、1-己基-3-甲基咪唑三氟甲磺酸盐、1-乙基-3-甲基咪唑双三氟甲基磺酰亚胺、1-正丁基-3-甲基咪唑六氟磷酸盐、1-乙基-3-甲基咪唑四氟硼酸盐或1-丁基-2,3-二甲基咪唑六氟磷酸盐。
3.如权利要求1所述的硼酸酯聚合物/离子液体复合导电凝胶，其特征在于：所述混合溶剂由DMSO和异丙醇以8:2的体积比混合而成。
4.权利要求1至3中任一权利要求所述的硼酸酯聚合物/离子液体复合导电凝胶的制备方法，其特征在于：包括如下步骤：
（1）将所述乙烯-乙烯醇共聚物与所述混合溶剂中的一部分于80-100 ℃下搅拌混合1-5 h，获得EVOH溶液；
（2）将单宁酸、离子液体、硼酸以及混合溶剂的另一部分于室温下搅拌混合1-3 h，获得交联剂溶液；
（3）将步骤（1）所得的EVOH溶液和步骤（2）所得的交联剂溶液混合均匀，冷却至室温下即得所述硼酸酯聚合物/离子液体复合导电凝胶。
5.如权利要求4所述的制备方法，其特征在于：所述EVOH溶液的浓度为20-30wt%。
6. 如权利要求4所述的制备方法，其特征在于：所述步骤（1）为：将所述乙烯-乙烯醇共聚物与所述混合溶剂中的一部分于95 ℃下搅拌混合3 h，获得EVOH溶液。
7.权利要求1至3中任一权利要求所述的硼酸酯聚合物/离子液体复合导电凝胶作为固态电解质的应用。
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| CN104681302A (zh) * | 2014-12-12 | 2015-06-03 | 宁波南车新能源科技有限公司 | 一种宽温高电压型超级电容器有机电解液及其制备方法 |
| CN108341948A (zh) * | 2017-01-25 | 2018-07-31 | 翁秋梅 | 一种杂化交联动态聚合物及其应用 |
| CN110628044B (zh) * | 2019-08-30 | 2020-08-25 | 厦门大学 | 一种三元交联水凝胶电解质、制备方法及其应用 |
| CN110628053B (zh) * | 2019-08-30 | 2021-04-20 | 厦门大学 | 一种聚乙烯醇-单宁酸-硼酸三元交联水凝胶、制备方法及应用 |
| KR102292189B1 (ko) * | 2019-10-23 | 2021-08-24 | 고려대학교 산학협력단 | 유기 이온 전도성 폴리머 겔 탄성체 및 이의 제조방법 |
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