CN111825070B - 一种原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料的制备方法 - Google Patents
一种原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料的制备方法 Download PDFInfo
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Abstract
本发明公开一种原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料的制备方法，首先将质量比为1:1.3的苯膦酸和六水合硝酸钴分别溶入无水乙醇和乙二醇体积比为2:3的混合溶剂中，然后，在150℃的条件下反应12‑48小时，制备了花状的苯基膦酸钴配位聚合物[Co(PhPO3)]前驱体；称取200mg Co(PhPO3)，在氮气氛围中，以2℃min‑1的升温速度从常温升至煅烧所需的温度(600‑1000℃)，并保持两小时，制备目标产物原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料(Co2P2O7/C‑X；其中X为煅烧的温度)。本发明提供的原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料的制备策略，实现了纳米Co2P2O7颗粒与纳米石墨化碳的原位杂化，有效的增强了材料的导电性和循环稳定性，具有良好的超级电容器应用潜能。
Description
技术领域
本发明属于功能性新材料技术领域，具体涉及一种原位杂化的，基于苯基膦酸钴配位聚合物的多孔花状Co2P2O7/C复合材料的可控制备方法及其电化学储能应用。
背景技术
随着电动汽车和移动电子设备的飞速发展，传统的储能装置已不能满足人们日益增长的生产需求，因此，开发安全、高效、便捷的储能装置，就显得尤为重要。超级电容器，作为一种新兴的电能存储器件，由于其具有循环寿命长、充放电速率快、安全系数高、功率密度大等优势，引起科学界的广泛关注。众所周知，根据电荷存储机制不同，超级电容器主要分为双电层超级电容器和赝电容超级电容器。其中，赝电容超级电容器是依靠电极材料与电解质溶液之间发生的氧化还原反应实现电荷存储，因此，通过设计和调整一些合适的电极材料，提高与电解质溶液之间的氧化还原反应活性，是提高赝电容超级电容器储能性能的策略之一。
过渡金属磷酸盐(TMPs,MxPyOz M＝Co2+,Ni2+,Mn2+,et al.)，是一种由磷酸盐/焦磷酸盐/磷阴离子和金属离子构建的结构稳定的具有开放骨架的一类材料。以Co2P2O7为例，该材料具有优越的氧化还原活性、丰富的自然储量和环境友好等优点，是一种十分有潜力的候选电极材料之一。然而，该材料本身的电子电导率较低，限制其储能性能。因此设计与构筑TMPs与高导电材料的复合材料，尤其是纳米级的复合与原位的掺杂，是解决材料本征电导性缺陷和提升电容器性能的有效途径。
配位聚合物，是一类由金属离子和有机配体通过自组装的方式，以配位键相互连接而成的聚合物网络结构。其具有结构和组成多样、超高的比表面积、丰富的孔结构以及孔径可调等优点，是一种制备超级电容器电极材料的理想前驱体。此外，配位聚合物独特的金属-有机杂化结构，可实现无机纳米粒子和纳米碳的原位杂化，增强复合材料电子电导率，促进电化学反应的动力学过程。因此，设计与制备具有特定形貌的配位聚合物前驱体，并通过可控的处理工艺，构筑原位碳掺杂的纳米过渡金属磷酸盐，可以显著改良过渡金属磷酸盐的本征缺陷，实现超级电容器性能的提高。
发明内容
本发明提供了一种原位杂化的策略，通过精准的制备工艺调控，基于花状的苯基膦酸钴配位聚合物[Co(PhPO3)]前驱体独特的配位骨架结构，通过高温热转化过程，保持了Co(PhPO3)前驱体的框架，防止了Co2P2O7纳米颗粒的过度团聚，实现了纳米Co2P2O7颗粒与纳米石墨化碳的原位杂化，有效的增强了焦磷酸钴的比容量和循环稳定性。
本发明提出的一种原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料的制备方法，可以通过如下技术路线予以实现：
(1)Co(PhPO3)前驱体的制备：将质量比为1:1.3的苯膦酸和六水合硝酸钴分别溶入无水乙醇和乙二醇体积比为2:3的混合溶剂中，超声分散30分钟使其混合均匀并形成均一溶液。之后将其转移到高压反应釜中，在150℃的条件下反应12-48小时；这里反应12～48小时是为了使Co(PhPO3)材料可以充分结晶并矿化，反应时间过短材料的结晶度和尺寸较小，反应时间增长材料结晶度和尺寸会逐渐增加。
(2)Co2P2O7/C杂化材料的制备：称取200mg Co(PhPO3)前驱体置于瓷舟，将瓷舟放入管式炉中，在氮气氛围中，以2℃min-1的升温速度从常温升至煅烧所需的温度(600-1000℃)，并在该温度下保持两个小时，制备目标产物原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料(Co2P2O7/C-X；其中X为煅烧的温度)；这里不同的煅烧温度会影响材料的形貌，结晶度，相转变程度等，温度过低时，材料无法完全转变为焦磷酸钴和石墨化的碳，温度过高时，前驱体的花状形貌难以维持，会破坏材料的纳米花状结构。
作为本发明的进一步特征：所述步骤(1)溶剂热反应时间为24小时,得到的Co(PhPO3)材料呈现由层状结构堆积出的花状形貌；虽然溶剂热反应不同时间得到的Co(PhPO3)的结晶性与纳米尺寸会有区别，对本发明的后续热转化过程也同样适用，只是性能会有所区别。
作为本发明的进一步特征：所述步骤(2)的煅烧温度为900℃，并命名为Co2P2O7/C-900。
作为本发明的进一步的特征：经过步骤(2)得到的原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料具有良好的超级电容器性能，在三电极体系条件下，其在1Ag-1的电流密度下的比容量达到248.2～349.6F g-1，其中最优样品Co2P2O7/C-900在2Ag-1的电流密度下，经过3000个循环后其容量保持率高达97.33％，表现出优异的循环稳定性。
作为本发明的进一步特征：经过步骤(2)原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料还可以与石墨烯基超级电容器负极材料组装构筑两电极超级电容器，其在0.375kW·kg-1功率密度下，能量密度高达21.9Wh·kg-1。
由于采用以上技术方案，本发明具有以下有益效果：
通过本发明制备的原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料，基于一种由有机苯环包覆无机2D[Co(-PO3)(H2O)2]n层组成的花状结构的苯基膦酸钴配位聚合物[Co(PhPO3)]前驱体。在氮气氛围中，通过高温煅烧过程，使前驱体的中的2D无机层转变为Co2P2O7纳米颗粒，同时2D无机层表面的有机苯环原位转变为石墨化的碳，覆盖在无机层表面，形成多孔花状Co2P2O7/C复合材料。其中，在氮气氛围下进行煅烧，隔绝氧气，可以保护材料中的有机苯环不被氧化。原位纳米级石墨化碳的形成，可以提高材料的电子电导率和循环稳定性，同时防止Co2P2O7纳米颗粒的过度团聚，提供更多的电化学活性位点，提高材料的比容量。所以，通过本发明方法制备的原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料具有更优良的超级电容器性能，具体的说，在1A g-1的电流密度下，它的比容量达到248.2～349.6F g-1，其中最优样品Co2P2O7/C-900在2Ag-1的电流密度下，3000个循环后其容量保持率高达97.33％，表现出优异的循环稳定性。
附图说明：
图1：实施例1中Co(PhPO3)前驱体的扫描电镜图；
图2：实施例1中Co(PhPO3)前驱体的粉末X-射线衍射图；
图3：实施例1中Co2P2O7/C-900的粉末X-射线衍射图；
图4：实施例1中Co2P2O7/C-900的扫描电镜图；
图5：实施例1中Co2P2O7/C-900的投射电镜图；
图6：实施例1中Co2P2O7/C-900的X-射线光电子能谱图；
图7：实施例1中Co2P2O7/C-900在不同扫速下的恒流充放电曲线图；
图8：实施例1中Co2P2O7/C-900在三电极体系中的循环稳定性测试曲线；
图9：实施例2中Co2P2O7-900在不同扫速下的恒流充放电曲线图；
图10：实施例3中Co2P2O7/C-600在不同扫速下的恒流充放电曲线图；
图11：实施例4中Co2P2O7/C-700在不同扫速下的恒流充放电曲线图；
图12：实施例5中Co2P2O7/C-800在不同扫速下的恒流充放电曲线图；
图13：实施例6中Co2P2O7/C-1000在不同扫速下的恒流充放电曲线图。
具体实施方式
下面结合具体实验方案和附图阐述本发明的技术特点，但本发明并不局限于此。下面实施例所述试验方法，如无特殊说明，均为常规方法；所述仪器及材料，如无特殊说明，均可从商业途径获得。
实施例1
一种原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料的制备方法，包括以下步骤：
(1)将质量比为1:1.3的苯膦酸和六水合硝酸钴分别溶入无水乙醇和乙二醇体积比为2:3的混合溶剂中，超声分散30分钟使其混合均匀并形成均一溶液。之后将其转移到高压反应釜中，在150℃的条件下反应24小时。待高压反应釜自然冷却至室温，收集得到的沉淀，用无水乙醇离心洗涤2～3次，然后在70℃的烘箱中干燥12小时，得到花状Co(PhPO3)前驱体。Co(PhPO3)前驱体的形貌如其扫描电镜图所示(图1)；Co(PhPO3)前驱体的结晶性如其粉末X-射线衍射图所示(图2)。
(2)称取200mg Co(PhPO3)前驱体置于瓷舟，将瓷舟放入管式炉中，在氮气氛围中，以2℃min-1的升温速度从常温升至900℃，并在900℃的温度下保持两个小时，制备Co2P2O7/C-900。Co2P2O7/C-900的结晶性如其粉末X-射线衍射图所示(图3)；Co2P2O7/C-900的形貌如其扫描电镜图所示(图4)，材料维持了前驱体的花状形貌，并且形成了一个多孔骨架；Co2P2O7/C-900的微观形貌如其投射电镜图所示(图5)，材料的多孔花状骨架由一些纳米粒子构建的纳米分支交错支撑而成；Co2P2O7/C-900的电子能谱如其XPS图所示(图6)，材料内部含有Co、P、C、O等元素，表明高温煅烧之后，碳元素得以成功保留。Co2P2O7/C-900在不同扫速下的恒流充放电如图7所示，通过计算得Co2P2O7/C-900在1Ag-1的电流密度下的比容量达到349.6F g-1，在2Ag-1的电流密度下，经过3000个循环后其容量保持率高达97.33％(图8)。
实施例2
一种原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料的制备方法，包括以下步骤：
(1)Co(PhPO3)前驱体的制备同实施例1。
(2)称取200mg Co(PhPO3)前驱体置于瓷舟，将瓷舟放入马弗炉中，在空气中，以2℃min-1的升温速度从常温升至900℃，并在900℃的温度下保持两个小时，制备Co2P2O7-900。Co2P2O7-900在不同扫速下的恒流充放电如图9所示，通过图中计算得Co2P2O7-900在1Ag-1的电流密度下的比容量达到234F g-1。
实施例3
一种原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料的制备方法，包括以下步骤：
(1)Co(PhPO3)前驱体的制备同实施例1。
(2)称取200mg Co(PhPO3)前驱体置于瓷舟，将瓷舟放入管式炉中，在氮气氛围中，以2℃min-1的升温速度从常温升至600℃，并在600℃的温度下保持两个小时，制备Co2P2O7/C-600。Co2P2O7/C-600在不同扫速下的恒流充放电如图10所示，通过图中计算得Co2P2O7/C-600在1A g-1的电流密度下的比容量达到248.2F g-1。
实施例4
一种原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料的制备方法，包括以下步骤：
(1)Co(PhPO3)前驱体的制备同实施例1。
(2)称取200mg Co(PhPO3)前驱体置于瓷舟，将瓷舟放入管式炉中，在氮气氛围中，以2℃min-1的升温速度从常温升至700℃，并在700℃的温度下保持两个小时，制备Co2P2O7/C-700。Co2P2O7/C-700在不同扫速下的恒流充放电如图11所示，通过图中计算得Co2P2O7/C-700在1Ag-1的电流密度下的比容量达到313.8F g-1。
实施例5
一种原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料的制备方法，包括以下步骤：
(1)Co(PhPO3)前驱体的制备同实施例1。
(2)称取200mg Co(PhPO3)前驱体置于瓷舟，将瓷舟放入管式炉中，在氮气氛围中，以2℃min-1的升温速度从常温升至800℃，并在800℃的温度下保持两个小时，制备Co2P2O7/C-800。Co2P2O7/C-800在不同扫速下的恒流充放电如图12所示，通过图中计算得Co2P2O7/C-800在1A g-1的电流密度下的比容量达到334.6F g-1。
实施例6
一种原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料的制备方法，包括以下步骤：
(1)Co(PhPO3)前驱体的制备同实施例1。
(2)称取200mg Co(PhPO3)前驱体置于瓷舟，将瓷舟放入管式炉中，在氮气氛围中，以2℃min-1的升温速度从常温升至1000℃，并在1000℃的温度下保持两个小时，制备Co2P2O7/C-1000。Co2P2O7/C-1000在不同扫速下的恒流充放电如图13所示，通过图中计算得Co2P2O7/C-1000在1A g-1的电流密度下的比容量达到281F g-1。
对本发明中所公开的实施方式的描述并非为了限制本发明的范围，而是用于描述本发明。相应地，本发明的范围不受以上实施方式的限制，而是由权利要求或其等同物进行限定。
Claims (5)
1.一种原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料的制备方法，其特征在于，包括以下步骤：
(1)Co(PhPO3)前驱体的制备：将质量比为1:1.3的苯膦酸和六水合硝酸钴分别溶入无水乙醇和乙二醇体积比为2:3的混合溶剂中，超声分散30分钟使其混合均匀并形成均一溶液。之后将其转移到高压反应釜中，在150℃的条件下反应12-48小时。
(2)Co2P2O7/C杂化材料的制备：称取200mg Co(PhPO3)前驱体置于瓷舟，将瓷舟放入管式炉中，在氮气氛围中，以2℃ min-1的升温速度从常温升至煅烧所需的温度(600-1000℃)，并在该温度下保持两个小时，制备目标产物原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料，所获得的多孔材料在1Ag-1的电流密度下的比容量达到248.2～349.6F g-1。
2.根据权利要求书1所述的制备方法，其特征在于：所述步骤(1)溶剂热反应时间为24小时
3.根据权利要求书1所述的制备方法，其特征在于：所述步骤(2)的煅烧温度为900℃。
4.根据权利要求书1所述的制备方法，其特征在于：所述步骤(2)当煅烧温度为900℃时，得到的Co2P2O7/C复合材料在2A g-1的电流密度下，经过3000个循环后其容量保持率高达97.33％。
5.根据权利要求书1所述的制备方法，其特征在于：经过步骤(2)得到的原位杂化的配位聚合物衍生多孔花状Co2P2O7/C复合材料还可以与石墨烯基超级电容器负极材料组装构筑两电极超级电容器，其在0.375kW·kg-1功率密度下，能量密度高达21.9Wh·kg-1。
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