CN110078900A - 一种高循环稳定性聚3,4-乙撑二氧噻吩电极材料及其制备方法 - Google Patents
一种高循环稳定性聚3,4-乙撑二氧噻吩电极材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种高循环稳定性聚3,4‑乙撑二氧噻吩电极材料及其制备方法，属于超级电容器用电极材料制备技术领域。所述电极材料是在水相体系中，以3,4‑乙撑二氧噻吩为单体，以三氯化铁为氧化剂，以苋菜红为表面活性剂和交联剂，经化学氧化聚合制备而成。本发明制备的电极材料不仅具有多孔交联片状结构，而且具有比电容较高、循环稳定性优异、制备工艺简便、制备过程绿色环保等优势，具有显著的经济价值和社会效益。
Description
技术领域
本发明属于超级电容器用电极材料制备技术领域，具体涉及一种高循环稳定性聚3,4-乙撑二氧噻吩电极材料及其制备方法。
背景技术
聚3,4-乙撑二氧噻吩（PEDOT）具有能隙小，电导率高，易制备以及环境稳定等特点，成为最有希望的超级电容器电极材料。但是3,4-乙撑二氧噻吩单体在水中溶解度较低，以及聚合过程中团聚严重，导致PEDOT电极材料比电容不高，限制了PEDOT在超级电容器用电极材料方面的应用。针对以上问题，人们常常利用水溶性聚合物或者有机质子酸（如对甲苯磺酸、樟脑磺酸等）等对PEDOT进行掺杂，以提高3,4-乙撑二氧噻吩单体的溶解度，调控PEDOT的分子形貌，从而提高PEDOT的电化学性能。江杰青（江杰清, 李巍, 刘东志, 田建华, 郭亚芳, 周雪琴; 聚(3,4-乙撑二氧噻吩)/樟脑磺酸复合材料的合成及电化学性能,精细化工, 2012, 29(6): 541-541.）以樟脑磺酸为掺杂剂、三氯化铁为氧化剂，通过化学氧化法合成了聚3,4-乙撑二氧噻吩/樟脑磺酸复合材料。研究表明，该复合材料具有良好的导电性能。但实际上，有机质子酸的掺杂不能够改变PEDOT极易团聚的问题，所制备的PEDOT复合材料依然呈现致密堆积的表观形貌，不利于电极材料与电解液的充分接触，导致活性物质的利用率较低，因而比电容和循环稳定性都不高。中国发明专利CN 108314780A以刚果红和有机酸作为掺杂剂，在表面活性剂的作用下，在水相中通过化学氧化聚合反应制备聚3,4-乙撑二氧噻吩粗品，再采用硫酸溶液进行后处理，制备聚3,4-乙撑二氧噻吩多孔电极材料。虽然所制备的电极材料具有较高的比电容和较好的循环稳定性，但是该电极材料的制备工艺复杂，生产成本较高。
发明内容
本发明针对现有技术中聚3,4-乙撑二氧噻吩团聚严重以及电化学性能较差这一问题，提供一种高循环稳定性聚3,4-乙撑二氧噻吩电极材料及其制备方法。本发明制备的电极材料不仅具有多孔交联片状结构，而且具有比电容较高、循环稳定性优异、制备工艺简便、制备过程绿色环保等优势，具有显著的经济价值和社会效益。
为实现上述目的，本发明采用如下技术方案：
一种高循环稳定性聚3,4-乙撑二氧噻吩电极材料是在水相体系中，以3,4-乙撑二氧噻吩为单体，以三氯化铁为氧化剂，以苋菜红为表面活性剂和交联剂，经化学氧化聚合制备而成。
所述高循环稳定性聚3,4-乙撑二氧噻吩电极材料的制备方法包括以下步骤：
（1）将1~3 g苋菜红加入到100~300 mL去离子水中，在室温下磁搅拌20~60 min，制备苋菜红溶液。向上述溶液中加入1.5~6 g 3,4-乙撑二氧噻吩，在室温下先磁搅拌20~60 min，再超声30~60 min，最后再磁搅拌10~30 min，制备3,4-乙撑二氧噻吩和苋菜红的混合液；
（2）向上述混合液中逐滴滴加12~90 mL三氯化铁盐酸溶液，在20~40 ℃下，磁搅拌反应24~48 h。反应结束后，向反应混合物中加入200~600 mL甲醇，在室温下磁搅拌30~60 min，静置12~24 h；经过滤、甲醇和去离子水交叉洗涤、60 ℃真空干燥24 h，制备所述高循环稳定性聚3,4-乙撑二氧噻吩电极材料。
所述三氯化铁盐酸溶液中，三氯化铁的浓度为2 mol/L，盐酸的浓度为0.02 mol/L，溶剂为去离子水。
本发明与现有技术相比具有以下优点：
（1）苋菜红分子中含有三个磺酸根离子，通过与PEDOT的硫原子进行配位作用，可以作为交联剂将PEDOT交联起来，形成稳定的多孔交联片状结构。在电化学循环稳定性测试中，这种结构不易破坏，从而提高PEDOT的电化学循环稳定性。
（2）苋菜红具有π共轭结构，当与PEDOT进行交联时，能够增加PEDOT的π-π共轭程度，有利于电荷的传输，从而提高PEDOT的比电容。另外，苋菜红还可以作为表面活性剂，提高3,4-乙撑二氧噻吩单体在水中的溶解度。
（3）本发明制备的聚3,4-乙撑二氧噻吩电极材料不仅具有明显的多孔交联片状结构，而且在电流密度为0.2 A/g、0.5 A/g、1 A/g和2 A/g时，比电容为141 F/g、136 F/g、130F/g和117 F/g，经过1000次循环之后，比电容保持率仍然达到96 %以上，即具有比电容较高和循环稳定性优异的特点，同时制备工艺简便、制备过程绿色环保，具有显著的经济价值和社会效益。
附图说明
图1为实施例1制备的高循环稳定性聚3,4-乙撑二氧噻吩电极材料的红外光谱图；
图2为实施例1制备的高循环稳定性聚3,4-乙撑二氧噻吩电极材料的扫描电镜图；
图3为对比例1制备的聚3,4-乙撑二氧噻吩的扫描电镜图。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
实施例1
（1）将2 g苋菜红加入到200 mL去离子水中，在室温下磁搅拌40 min，制备苋菜红溶液。向上述溶液中加入3.5 g 3,4-乙撑二氧噻吩，在室温下先磁搅拌40 min，再超声45 min，最后再磁搅拌20 min，制备3,4-乙撑二氧噻吩和苋菜红的混合液；
（2）向上述混合液中逐滴滴加40 mL三氯化铁盐酸溶液，在30 ℃下，磁搅拌反应36 h。反应结束后，向反应混合物中加入400 mL甲醇，在室温下磁搅拌45 min，静置18 h。经过滤、甲醇和去离子水交叉洗涤、60 ℃真空干燥24 h，制备所述高循环稳定性聚3,4-乙撑二氧噻吩电极材料。
图1为本实施例制备的高循环稳定性聚3,4-乙撑二氧噻吩电极材料的红外光谱图。从图中可以看出，1625 cm-1和1369 cm-1处的峰分别对应噻吩环上C=C和C-C的不对称伸缩振动吸收峰，证明成功制备了聚3,4-乙撑二氧噻吩。1098 cm-1和543 cm-1处的峰为磺酸根基团的特征吸收峰，并且在3470 cm-1处出现的较大吸收峰来源于苋菜红分子内羟基的伸缩振动，这些都表明苋菜红成功交联进入聚3,4-乙撑二氧噻吩。
图2为本实施例制备的高循环稳定性聚3,4-乙撑二氧噻吩电极材料的扫描电镜图。图中显示，本发明制备的聚3,4-乙撑二氧噻吩呈现明显的多孔交联片状结构。这是因为苋菜红分子中含有三个磺酸根离子，通过与PEDOT的硫原子进行配位作用，可以作为交联剂将PEDOT交联起来，形成稳定的多孔交联片状结构。
实施例2
（1）将1 g苋菜红加入到100 mL去离子水中，在室温下磁搅拌20 min，制备苋菜红溶液。向上述溶液中加入1.5 g 3,4-乙撑二氧噻吩，在室温下先磁搅拌20 min，再超声30 min，最后再磁搅拌10 min，制备3,4-乙撑二氧噻吩和苋菜红的混合液；
（2）向上述混合液中逐滴滴加12 mL三氯化铁盐酸溶液，在20 ℃下，磁搅拌反应48 h。反应结束后，向反应混合物中加入200 mL甲醇，在室温下磁搅拌30 min，静置12 h。经过滤、甲醇和去离子水交叉洗涤、60 ℃真空干燥24 h，制备所述高循环稳定性聚3,4-乙撑二氧噻吩电极材料。
实施例3
（1）将3 g苋菜红加入到300 mL去离子水中，在室温下磁搅拌60 min，制备苋菜红溶液。向上述溶液中加入6 g 3,4-乙撑二氧噻吩，在室温下先磁搅拌60 min，再超声60 min，最后再磁搅拌30 min，制备3,4-乙撑二氧噻吩和苋菜红的混合液；
（2）向上述混合液中逐滴滴加90 mL三氯化铁盐酸溶液，在40 ℃下，磁搅拌反应24 h。反应结束后，向反应混合物中加入600 mL甲醇，在室温下磁搅拌60 min，静置24 h。经过滤、甲醇和去离子水交叉洗涤、60 ℃真空干燥24 h，制备所述高循环稳定性聚3,4-乙撑二氧噻吩电极材料。
对比例1
（1）将3.5 g 3,4-乙撑二氧噻吩加入到200 mL去离子水中，在室温下先磁搅拌40 min，再超声45 min，最后再磁搅拌20 min，制备3,4-乙撑二氧噻吩的分散液；
（2）向上述分散液中逐滴滴加40 mL三氯化铁盐酸溶液，在30 ℃下，磁搅拌反应36 h。反应结束后，向反应混合物中加入400 mL甲醇，在室温下磁搅拌45 min，静置18 h。经过滤、甲醇和去离子水交叉洗涤、60 ℃真空干燥24 h，制备聚3,4-乙撑二氧噻吩电极材料。
图3为本实施例制备的聚3,4-乙撑二氧噻吩的扫描电镜图。图中显示，没有添加苋菜红时，聚合生成的聚3,4-乙撑二氧噻吩呈现粗糙的大量块状固体堆积的表面形貌且空隙较少。
对比例2
（1）将1.5 g 3,4-乙撑二氧噻吩加入到100 mL去离子水中，在室温下先磁搅拌20 min，再超声30 min，最后再磁搅拌10 min，制备3,4-乙撑二氧噻吩的分散液；
（2）向上述分散液中逐滴滴加12 mL三氯化铁盐酸溶液，在20 ℃下，磁搅拌反应48 h。反应结束后，向反应混合物中加入200 mL甲醇，在室温下磁搅拌30 min，静置12 h。经过滤、甲醇和去离子水交叉洗涤、60 ℃真空干燥24 h，制备聚3,4-乙撑二氧噻吩电极材料。
对比例3
（1）将6 g 3,4-乙撑二氧噻吩加入到300 mL去离子水中，在室温下先磁搅拌60 min，再超声60 min，最后再磁搅拌30 min，制备3,4-乙撑二氧噻吩的分散液；
（2）向上述分散液中逐滴滴加90 mL三氯化铁盐酸溶液，在40 ℃下，磁搅拌反应24 h。反应结束后，向反应混合物中加入600 mL甲醇，在室温下磁搅拌60 min，静置24 h。经过滤、甲醇和去离子水交叉洗涤、60 ℃真空干燥24 h，制备聚3,4-乙撑二氧噻吩电极材料。
将质量百分比80 %产物、15 %乙炔炭黑和5 %聚偏氟乙烯混合均匀涂在不锈钢网上作为工作电极，以铂丝作为对电极，以饱和甘汞电极作为参比电极，以1 mol/L硫酸水溶液作为电解液，利用恒流充放电方法测试实施例和对比例所制备产物的比电容，利用循环伏安法测试实施例和对比例所制备产物的循环稳定性，其中，电压范围为-0.2~0.8 V，充放电电流密度分别0.2 A/g、0.5 A/g、1 A/g和2 A/g，扫描速率为100 mV/s。测试结果如下表1所示。
表1 性能测试结果
从实施例和对比例的测试结果可以看出，将苋菜红添加到聚3,4-乙撑二氧噻吩的聚合反应体系中，不仅可以提高聚3,4-乙撑二氧噻吩的比电容，而且可以显著提高聚3,4-乙撑二氧噻吩的循环稳定性。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (3)
1.一种高循环稳定性聚3,4-乙撑二氧噻吩电极材料，其特征在于：所述电极材料是在水相体系中，以3,4-乙撑二氧噻吩为单体，以三氯化铁为氧化剂，以苋菜红为表面活性剂和交联剂，经化学氧化聚合制备而成。
2.一种如权利要求1所述的高循环稳定性聚3,4-乙撑二氧噻吩电极材料的制备方法，其特征在于：包括以下步骤：
（1）将1~3 g苋菜红加入到100~300 mL去离子水中，在室温下磁搅拌20~60 min，制备苋菜红溶液；向上述溶液中加入1.5~6 g 3,4-乙撑二氧噻吩，在室温下先磁搅拌20~60 min，再超声30~60 min，最后再磁搅拌10~30 min，制备3,4-乙撑二氧噻吩和苋菜红的混合液；
（2）向上述混合液中逐滴滴加12~90 mL三氯化铁盐酸溶液，在20~40 ℃下，磁搅拌反应24~48 h；反应结束后，向反应混合物中加入200~600 mL甲醇，在室温下磁搅拌30~60 min，静置12~24 h；经过滤、甲醇和去离子水交叉洗涤、60 ℃真空干燥24 h，制备所述高循环稳定性聚3,4-乙撑二氧噻吩电极材料。
3.根据权利要求2所述的高循环稳定性聚3,4-乙撑二氧噻吩电极材料的制备方法，其特征在于：所述三氯化铁盐酸溶液中，三氯化铁的终浓度为2 mol/L，盐酸的终浓度为0.02mol/L，溶剂为去离子水。
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