CN110184744B - 一种结晶型聚芳醚酮纳米纤维膜、制备方法及其应用 - Google Patents
一种结晶型聚芳醚酮纳米纤维膜、制备方法及其应用 Download PDFInfo
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Abstract
一种结晶型聚芳醚酮纳米纤维膜、制备方法及其应用，属于静电纺丝技术领域。本发明利用静电纺丝技术，采用可溶性聚芳醚酮——聚芳醚酮‑1，3‑二氧戊环或聚芳醚酮亚胺溶液，制备结晶型聚芳醚酮纳米纤维膜。本发明所述方法操作简单，无需外部助剂，成本低廉，可规模化生产，突破了聚芳醚酮在有机溶剂中不能溶解带来的加工方法的限制，保留了结晶型聚芳醚酮的耐热、耐辐射、耐化学腐蚀、耐疲劳、耐冲击、抗蠕变、耐磨损、良好的阻燃性和优异的力学性能。本发明制备的结晶型聚芳醚酮纳米纤维膜具有可控的纤维直径和厚度，无需外部助剂和高温处理，能在严苛条件下正常使用，可在燃料电池、超级电容器及锂离子电池中到得应用。
Description
技术领域
本发明属于静电纺丝技术领域，具体涉及一种结晶型聚芳醚酮纳米纤维膜、制备方法及其应用。
背景技术
静电纺丝技术以设备简单、成本低廉、工艺成熟等优点成为制备纳米纤维材料的重要手段。不仅大多数高聚物可通过静电纺丝制备成纳米纤维，而且无机物、有机物和无机物等复合物也可以通过静电纺丝制备成纳米纤维集合体。这种适应性强、纤维结构可控、操作简单的纳米纤维制备工艺，广泛适用于生物医用、过滤、防护、催化、电子器件和纺织等领域。
聚芳醚酮是一类半结晶型、热塑性的高性能聚合物，主链由醚键，羰基和苯环组成，具有耐热等级高、耐辐射、耐化学腐蚀、耐疲劳、耐冲击、抗蠕变、耐磨损、良好的阻燃性和优异的力学性能。它们的熔点大于等于334℃，玻璃化转变温度大于等于143℃。由于其优异的综合性能，它们是一类具有广阔应用前景的高分子膜材料基体。然而，优异的耐溶剂性限制了它们加工成型方法的多样性，阻碍了其在实际应用中的广泛实用性。许多研究和应用通过对其改性而破坏其结晶性或利用浓硫酸对其溶解，但聚芳醚酮的耐溶剂性和机械强度强烈依赖于它们的结晶行为，在改性或硫酸溶解过程中，聚芳醚酮结晶性被破坏，这大大降低了其综合性能和使用性能。
中国专利(CN107611322A)公开了一种高强度锂电池隔膜及其生产工艺：将卤代甲酮类化合物与双羟基类化合物通过聚合反应合成聚醚醚酮,经熔融挤出得到聚醚醚酮纳米纤维膜并在高温下拉伸形成高强度锂电池隔膜。然而这种方法不仅需要在高温下进行，增加了工艺成本和操作难度，难以控制纤维直径和孔隙率，而且更不利的是，与本发明中的静电纺丝聚醚醚酮纳米纤维膜相比，所得到的聚合物失去了聚醚醚酮原本的结晶性。根据高分子物理的理论，分子的对称性越高越容易形成结晶，而该发明中聚合物侧链甲基结构的存在使其具有不对称性，因而其制备的纳米纤维膜不具备结晶性，不耐溶剂和高温，会影响在实际应用中的综合性能。
因此，设计发明具有结晶性的聚芳醚酮纳米纤维膜功能材料将会克服一些不足，发挥其高性能，拓展其更广泛和苛刻的应用领域。
发明内容
本发明的目的是提供一种结晶型聚芳醚酮纳米纤维膜、制备方法及其应用，以克服聚芳醚酮加工成型和应用受限的问题，促进其在生物医用、过滤、防护、催化、能源和光电等领域的应用。
本发明利用静电纺丝技术，采用可溶性聚芳醚酮——聚芳醚酮-1，3-二氧戊环或聚芳醚酮亚胺，制备结晶型聚芳醚酮纳米纤维膜。该方法操作简单，无需外部助剂，成本低廉，可规模化生产。
以聚醚醚酮为例，聚醚醚酮-1,3-二氧戊环的反应式如下所示：
以聚醚醚酮为例，聚醚醚酮亚胺的反应式如下所示：
或
n为正整数，表示聚合度。
本发明所述的一种结晶型聚芳醚酮纳米纤维膜的制备方法，其步骤如下：
(1)将聚芳醚酮-1,3-二氧戊环或聚芳醚酮亚胺前驱体溶解于极性聚合物良溶剂中，溶液质量浓度为15～25％，室温下密闭搅拌10～20小时，制备得到澄清透明的纺丝液；
(2)将步骤(1)所述纺丝液装在静电纺丝装置的注射器中，注射器针头与高压电源的正极相连，铝箔接收板与高压电源的负极相连，进行纺丝，在铝箔接收板上得到纳米纤维膜；
(3)将步骤(2)得到的纳米纤维膜浸泡在质子酸中，酸化24～48小时，而后用去离子水冲洗，除去过量的酸，于60～120℃、真空下烘干，得到聚芳醚酮纳米纤维膜；
(4)将步骤(3)得到的聚芳醚酮纳米纤维膜于80～220℃热处理4～8小时使其结晶，得到本发明所述的结晶型聚芳醚酮纳米纤维膜。
其中，所述的极性聚合物良溶剂为NMP、DMAc或DMF。
其中，步骤(2)所述的注射器针头与铝箔接收板上表面的距离为10～20cm，施加电压为10～25kV，注射器推进速度为0.01～0.5mL/h。
其中，步骤(3)所述的质子酸为盐酸、硫酸、硝酸、醋酸、三氟乙酸、苯磺酸、甲磺酸或三氟甲磺酸。
本发明实施例提供了所述的结晶型聚芳醚酮纳米纤维膜在燃料电池、超级电容器及锂离子电池中的用途实例。
与现有技术相比，本发明的结晶型聚芳醚酮纳米纤维膜具有可控的纤维直径和厚度，其直径为110～190nm，膜的厚度为10～100μm，无需外部助剂和高温处理，能在严苛条件下正常使用。其突出效果在于，突破了聚芳醚酮在有机溶剂中不能溶解带来的加工方法的限制，保留了结晶型聚芳醚酮的耐热、耐辐射、耐化学腐蚀、耐疲劳、耐冲击、抗蠕变、耐磨损、良好的阻燃性和优异的力学性能，制备过程简单易行，无需外部助剂，原料成本低廉、可回收，可规模化生产，广泛适用于生物医用材料、过滤、防护、催化、能源和光电等领域。
附图说明
图1：实施例1～3制备的聚醚醚酮-1,3-二氧戊环还原得到的聚醚醚酮纳米纤维膜的DSC曲线；该图可说明聚醚醚酮纳米纤维膜的熔点和结晶峰，表明成功将聚醚醚酮-1,3-二氧戊环还原为结晶型聚醚醚酮。
图2：实施例4制备的聚醚醚酮亚胺还原得到的聚醚醚酮纳米纤维膜的DSC 曲线；该图可说明聚醚醚酮纳米纤维膜的熔点和结晶峰，表明成功将聚醚醚酮亚胺还原为结晶型聚醚醚酮。
图3：实施例1～3制备的聚醚醚酮-1,3-二氧戊环还原得到的聚醚醚酮纳米纤维膜的SEM图片；该图表明了纳米纤维膜的成功制备，其中纤维直径为110nm，膜的厚度为10μm。
图4：实施例4制备的聚醚醚酮亚胺还原得到的聚醚醚酮纳米纤维膜的SEM 图片；该图表明了纳米纤维膜的成功制备，其中纤维直径为190nm，膜的厚度为 100μm。
图5：实施例1制备的燃料电池隔膜在高浓度(10mol/L)甲醇下的电池性能曲线；该图说明基于聚醚醚酮纳米纤维膜制备的燃料电池复合隔膜具有较高的开路电压(0.53V)和功率密度(35mW/cm2)，表现出良好的单电池性能。
图6：实施例2制备的超级电容器常规凝胶电解质(GPE-20)和交联型凝胶电解质(NGPE-CL-20)的线性扫描伏安曲线；该图表明NGPE-CL-20和GPE-20 在0.0到2.0V之间的电位下都是稳定的，具有较宽的电位窗口，能保证在高电位下的长期稳定性。
图7：实施例3制备的锂离子电池隔膜(PEEK)与商业的锂离子电池隔膜 (Cel2325)的倍率性能曲线；该图表明用聚醚醚酮膜组装的电池与商业隔膜相比具有更好的倍率性能，这是因为其具有高孔隙率、高电解质吸收、高电解质润湿性和更高的离子电导率。
具体实施方式
下面通过具体实施例对本发明的方法进行说明，所述的实施例只是对本发明的权利要求的具体描述，权利要求包括但不限于所述的实施例内容。
下述实施例中所述的试剂和材料如无特殊说明，均从商业途径获得；所述实验方法，如无特殊说明，均为常规方法。
实施例1
将可溶性聚醚醚酮前驱体：聚醚醚酮-1,3-二氧戊环(其制备方法见文献[1,2])(1.0g)溶解于极性聚合物良溶剂NMP(4mL)中，溶液质量浓度为20％，室温下密闭搅拌15小时，制备得到澄清透明的纺丝液；将纺丝液装在静电纺丝装置的注射器中，注射器针头与高压电源的正极相连，铝箔接收板与高压电源的负极相连，进行纺丝，制备的纳米纤维膜形成于铝箔接收板上；注射器针头与铝箔接收板上表面的距离为15cm，施加电压为15kV，注射器推进速度为0.2mL/h。将得到的纳米纤维膜浸泡在盐酸中，酸化28小时，而后用去离子水冲洗，除去过量的盐酸，于60℃真空烘干，然后在200℃热处理6小时，使其结晶。然后将制备的结晶型聚醚醚酮纳米纤维膜按照文献[3]组装成燃料电池膜电极组件进行单电池性能测试，利用Arbin燃料电池工作站在10mol/L甲醇水溶液中于70℃条件下测试。
实施例1制备的聚醚醚酮-1,3-二氧戊环还原得到的聚醚醚酮纳米纤维膜的 SEM图片见附图3；该图表明了纳米纤维膜的成功制备，其中纤维直径为110nm，膜的厚度为10μm。实施例1所制备的燃料电池隔膜在高浓度(10mol/L)甲醇下的电池性能曲线见附图7；该图说明基于聚醚醚酮纳米纤维膜制备的燃料电池复合隔膜具有较高的开路电压(0.53V)和功率密度(35mW/cm2)，具有良好的单电池性能。
实施例2
与实施例1所述结晶型聚醚醚酮纳米纤维膜的制备过程相同，只是将制备的结晶型聚醚醚酮纳米纤维膜按照文献[4]组装成超级电容器进行循环伏安曲线测试，利用电化学工作站(CHI 660A)在0.0～3.0V的电压范围内、扫描速率为5 mV s-1、环境温度下测试。
实施例2制备的聚醚醚酮-1,3-二氧戊环还原得到的聚醚醚酮纳米纤维膜的 SEM图片见附图3；该图表明了纳米纤维膜的成功制备，其中纤维直径为110nm，膜的厚度为10μm。实施例2所制备的超级电容器常规凝胶电解质(GPE-20)和交联型凝胶电解质(NGPE-CL-20)的线性扫描伏安曲线见附图6；该图表明 NGPE-CL-20和GPE-20在0.0到2.0V之间的电位下都是稳定的，具有较宽的电位窗口，能保证在较高电位下的长期稳定性。
实施例3
与实施例1所述结晶型聚醚醚酮纳米纤维膜的制备过程相同，只是将制备的结晶型聚醚醚酮纳米纤维膜按照文献[5]组装成锂离子纽扣电池进行循环性能的测试，利用恒电位仪(Solartron Analytical)在3C、55℃的条件下测试。
实施例3制备的聚醚醚酮-1,3-二氧戊环还原得到的聚醚醚酮纳米纤维膜的 SEM图片见附图3；该图表明了纳米纤维膜的成功制备，其中纤维直径为110nm，膜的厚度为10μm。实施例3所制备的锂离子电池隔膜(PEEK)与商业的锂离子电池隔膜(Cel 2325)的倍率性能见附图7；该图表明用聚醚醚酮膜组装的电池与商业隔膜相比具有更好的倍率性能，这是因为其具有高孔隙率、高电解质吸收、高电解质润湿性和更高的离子电导率。
实施例4
如实施例1～3所述，只是将聚醚醚酮-1,3-二氧戊环更换成聚醚醚酮亚胺(其制备方法见文献[6,7])，也制备得到了结晶型聚醚醚酮纳米纤维膜。
实施例4制备的聚醚醚酮亚胺还原得到的聚醚醚酮纳米纤维膜的SEM图片见附图4；该图表明了纳米纤维膜的成功制备，其中纤维直径为190nm，膜的厚度为100μm。
实施例5
如实施例1～4所述，只是将溶剂更换为DMAc或DMF，也制备得到了结晶型聚醚醚酮纳米纤维膜。
实施例6
如实施例1～5所述，只是将盐酸更换硫酸、硝酸、醋酸、三氟乙酸、苯磺酸、甲磺酸或三氟甲磺酸，也制备得到了结晶型聚醚醚酮纳米纤维膜。
参考文献：
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Claims (6)
1.一种结晶型聚芳醚酮纳米纤维膜的制备方法，其步骤如下：
(1)将聚芳醚酮-1,3-二氧戊环或聚芳醚酮亚胺溶解于极性聚合物良溶剂中，溶液质量浓度为15～25％，室温下密闭搅拌10～20小时，制备得到澄清透明的纺丝液；
(2)将步骤(1)所述纺丝液装在静电纺丝装置的注射器中，注射器针头与高压电源的正极相连，铝箔接收板与高压电源的负极相连，进行纺丝，在铝箔接收板上得到纳米纤维膜；
(3)将步骤(2)得到的纳米纤维膜浸泡在质子酸中，酸化24～48小时，而后用去离子水冲洗，除去过量的酸，于60～120℃、真空下烘干，得到聚芳醚酮纳米纤维膜；
(4)将步骤(3)得到的聚芳醚酮纳米纤维膜于80～220℃热处理4～8小时使其结晶，得到结晶型聚芳醚酮纳米纤维膜。
2.如权利要求1所述的一种结晶型聚芳醚酮纳米纤维膜的制备方法，其特征在于：步骤(1)中所述的极性聚合物良溶剂为NMP、DMAc或DMF。
3.如权利要求1所述的一种结晶型聚芳醚酮纳米纤维膜的制备方法，其特征在于：步骤(2)中所述的注射器针头与铝箔接收板上表面的距离为10～20cm，施加电压为10～25kV，注射器推进速度为0.01～0.5mL/h。
4.如权利要求1所述的一种结晶型聚芳醚酮纳米纤维膜的制备方法，其特征在于：步骤(3)中所述的质子酸为盐酸、硫酸、硝酸、醋酸、三氟乙酸、苯磺酸、甲磺酸或三氟甲磺酸。
5.一种结晶型聚芳醚酮纳米纤维膜，其特征在于：是由权利要求1～4任何一项所述的方法制备得到。
6.权利要求1所述的一种结晶型聚芳醚酮纳米纤维膜在燃料电池、超级电容器或锂离子电池中的应用。
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