CN107492451A - 多孔结构钴酸锌‑石墨烯复合活性材料/泡沫镍超级电容器电极的制备方法 - Google Patents
多孔结构钴酸锌‑石墨烯复合活性材料/泡沫镍超级电容器电极的制备方法 Download PDFInfo
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Abstract
本发明公开了一种多孔结构钴酸锌‑石墨烯复合活性材料/泡沫镍超级电容器电极的制备方法，属于超级电容器电极的制备技术领域。本发明的技术方案要点为：将氧化石墨烯和P123超声分散在尿素水溶液中形成均匀分散液，再向该分散液中加入硝酸钴和乙酸锌形成均匀前驱体溶液，然后将该前驱体溶液转移至水热反应釜中，同时将泡沫镍放入到水热反应釜内前驱体溶液中，于90‑150℃水热反应在泡沫镍集流体表面沉积钴锌氢氧化物‑石墨烯复合物，超声洗涤并干燥后转移至马弗炉中，在空气气氛中于250℃煅烧制得多孔结构钴酸锌‑石墨烯复合活性材料/泡沫镍超级电容器电极。本发明制作方法简单，易于控制，成本较低，可望以较大规模制作高性能的超级电容器。
Description
技术领域
本发明属于超级电容器电极的制备技术领域，具体涉及一种多孔结构钴酸锌-石墨烯复合活性材料/泡沫镍超级电容器电极的制备方法。
背景技术
随着化石能源消费的不断增加和日益加剧的环境压力，绿色高效的能源器件研究开发备受重视。超级电容器是一类重要的电化学储能器件，具有高功率密度、短充放电时间和长循环寿命等优势，应用前景非常广阔。依据储能机制，超级电容器可分为双电层电容器和赝电容型电容器，其中赝电容型电容器主要通过电极自身的氧化还原反应储存电荷，其工作原理类似于传统二次电池，因而具有较高的比容和能量密度。电极材料自身的氧化还原活性是决定赝电容型电容器储能性能的关键因素，一些具有较高氧化还原活性的过渡金属氧化物如RuO2、MnO2、Co3O4等具有较高理论比容，是常用的赝电容活性电极材料。由不同过渡金属组成的复合氧化物具有不同的微观结构和能带结构，因而具有更优越的氧化还原活性，也可用作高性能赝电容活性材料，在近些年受到广泛关注。
钴酸锌是一类重要的尖晶石型双金属复合氧化物，在锂离子电池、锂空电池及超级电容器中广泛用作电极材料。由于复合物中的元素钴能通过氧化还原反应提供显著的赝电容，因此具有优越的赝电容特性。此外该复合氧化物中的金属元素毒性较低，可用作高效安全的赝电容活性材料，进而通过与低维导电碳质材料复合，在碳基体表面构建多级结构框架，提高复合材料可接触表面积和电子离子导电性，能进一步改善电极材料的电容性能。但是目前为止，有关钴酸锌与碳质基体复合物的研究开发报道较少，采取简便高效合成工艺制备多孔结构钴酸锌与碳质基体复合物电极对绿色高效超级电容器的开发应用有积极意义。
发明内容
本发明解决的技术问题是提供了一种多孔结构钴酸锌-石墨烯复合活性材料/泡沫镍超级电容器电极的制备方法，该方法所制得的钴酸锌-石墨烯复合活性材料/泡沫镍超级电容器电极能够提供优越的电容性能。
本发明为解决上述技术问题采用如下技术方案，多孔结构钴酸锌-石墨烯复合活性材料/泡沫镍超级电容器电极的制备方法，其特征在于具体步骤为：将氧化石墨烯和嵌段聚合物表面活性剂P123超声分散在尿素水溶液中形成均匀分散液，再向该分散液中加入硝酸钴和乙酸锌形成均匀前驱体溶液，然后将该前驱体溶液转移至水热反应釜中，同时将泡沫镍放入到水热反应釜内前驱体溶液中，于90-150℃水热反应在泡沫镍集流体表面沉积钴锌氢氧化物-石墨烯复合物，超声洗涤并干燥后转移至马弗炉中在空气气氛中于250℃煅烧制得多孔结构钴酸锌-石墨烯复合活性材料/泡沫镍超级电容器电极。
进一步优选，所述氧化石墨烯与嵌段聚合物表面活性剂P123的质量比为1:5，尿素溶液的摩尔浓度为0.025mol/L，尿素溶液与氧化石墨烯的投料配比为1mL:1mg，硝酸钴和乙酸锌的总摩尔量与氧化石墨烯的投料配比为1×10-3mol:10mg，硝酸钴与乙酸锌的摩尔比为1:3-3:1，泡沫镍基底的尺寸为1cm×1cm×0.1cm。
本发明制得的多孔结构钴酸锌-石墨烯复合活性材料具有较高的比表面积，有利于电解质离子的充分吸附，复合活性材料呈现出显著的赝电容，因而能提供较高比容。同时，该复合活性材料的多孔结构能提供高效离子扩散通道和良好导电性，直接沉积的活性物质能与泡沫镍集流体紧密接触，可避免传统电极制作过程中粘结剂的使用，其较高的离子和电子导电性有助于获得较高的倍率性能，适合大电流充放电。此外，该多孔结构钴酸锌-石墨烯复合活性材料/泡沫镍超级电容器电极的制作方法简单，易于控制，成本较低，可望以较大规模制作高性能的超级电容器。
附图说明
图1为本发明实施例2制得活性电极的扫描电镜图；
图2为本发明实施例2制得活性电极在2mol/L KOH电解质中不同电流密度下的充放电曲线。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1
将40mg氧化石墨烯和200mg P123超声分散在40mL 0.025mol/L的尿素水溶液中形成分散液，再向该分散液中加入2×10-3mol硝酸钴和2×10-3mol乙酸锌，搅拌形成均匀前驱体溶液，然后将该前驱体溶液转移至水热反应釜中，同时将尺寸为1cm×1cm×0.1cm的泡沫镍放入到水热反应釜内前驱体溶液中，于90℃水热反应5h在泡沫镍集流体表面沉积钴锌氢氧化物-石墨烯复合物，超声洗涤并干燥后转移至马弗炉中，在空气气氛中于250℃煅烧2h制得多孔结构钴酸锌-石墨烯复合活性材料/泡沫镍活性电极。将制得活性电极浸入2mol/L KOH电解质中作为工作电极，HgO/Hg电极作为参比电极，铂箔电极作为对电极，组装三电极体系，测得该活性电极在1A/g的比容为2532F/g，在1-20A/g电流密度范围内，比容保持率为34%。
实施例2
将40mg氧化石墨烯和200mg P123超声分散在40mL 0.025mol/L的尿素水溶液中形成分散液，再向该分散液中加入3×10-3mol硝酸钴和1×10-3mol乙酸锌，搅拌形成均匀前驱体溶液，然后将该前驱体溶液转移至水热反应釜中，同时将尺寸为1cm×1cm×0.1cm的泡沫镍放入到水热反应釜内前驱体溶液中，于120℃水热反应5h在泡沫镍集流体表面沉积钴锌氢氧化物-石墨烯复合物，超声洗涤并干燥后转移至马弗炉中，在空气气氛中于250℃煅烧2h制得黑色多孔结构钴酸锌-石墨烯复合活性物质/泡沫镍活性电极（图1）。将制得活性电极按照实施例1组装三电极体系测试电化学性能，该电极在1A/g的比容为3222F/g（图2），在1-20A/g电流密度范围内，比容保持率为49%。
实施例3
将40mg氧化石墨烯和200mg P123超声分散在40mL 0.025mol/L的尿素水溶液中形成分散液，再向该分散液中加入1×10-3mol硝酸钴和3×10-3mol乙酸锌，搅拌形成均匀前驱体溶液，然后将该前驱体溶液转移至水热反应釜中，同时将尺寸为1cm×1cm×0.1cm的泡沫镍放入到水热反应釜内前驱体溶液中，于150℃水热反应5h在泡沫镍集流体表面沉积钴锌氢氧化物-石墨烯复合物，超声洗涤并干燥后转移至马弗炉中，在空气气氛中于250℃煅烧2h制得多孔结构钴酸锌-石墨烯复合活性物质/泡沫镍活性电极。复合活性材料中钴酸锌片层在石墨烯表面交联组装形成多孔结构框架，能提供较高比表面积和高效离子扩散通道，有利于获得较高比容和倍率性能。将制得活性电极按照实施例1组装三电极体系测试电化学性能，该活性电极在1A/g的比容为1306F/g，1-20A/g电流密度范围内，比容保持率为43%。
实施例4
将200mg P123超声分散在40mL 0.025mol/L的尿素水溶液中形成分散液，再向该分散液中加入2×10-3mol硝酸钴和2×10-3mol乙酸锌，搅拌形成均匀前驱体溶液，然后将该前驱体溶液转移至水热反应釜中，同时将尺寸为1cm×1cm×0.1cm的泡沫镍放入到水热反应釜内前驱体溶液中，于120℃水热反应8h在泡沫镍集流体表面沉积钴锌氢氧化物，超声洗涤并干燥后转移至马弗炉中在空气气氛中于250℃煅烧2h制得钴锌氧化物/泡沫镍活性电极。将制得的活性电极按照实施例1组装三电极体系测试电化学性能，该电极在1A/g的比容为1514F/g，在1-20A/g电流密度范围内，比容保持率为25%。
通过以上实施例可以看出，通过引入氧化石墨烯，改变硝酸钴与乙酸锌的比例以及水热处理温度、时间等制备参数，能有效调控电极比电容和倍率性能。
以上实施例描述了本发明的基本原理、主要特征及优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明原理的范围下，本发明还会有各种变化和改进，这些变化和改进均落入本发明保护的范围内。
Claims (2)
1.多孔结构钴酸锌-石墨烯复合活性材料/泡沫镍超级电容器电极的制备方法，其特征在于具体步骤为：将氧化石墨烯和嵌段聚合物表面活性剂P123超声分散在尿素水溶液中形成均匀分散液，再向该分散液中加入硝酸钴和乙酸锌形成均匀前驱体溶液，然后将该前驱体溶液转移至水热反应釜中，同时将泡沫镍放入到水热反应釜内前驱体溶液中，于90-150℃水热反应在泡沫镍集流体表面沉积钴锌氢氧化物-石墨烯复合物，超声洗涤并干燥后转移至马弗炉中在空气气氛中于250℃煅烧制得多孔结构钴酸锌-石墨烯复合活性材料/泡沫镍超级电容器电极。
2.根据权利要求1所述的多孔结构钴酸锌-石墨烯复合活性材料/泡沫镍超级电容器电极的制备方法，其特征在于：所述氧化石墨烯与嵌段聚合物表面活性剂P123的质量比为1:5，尿素溶液的摩尔浓度为0.025mol/L，尿素溶液与氧化石墨烯的投料配比为1mL:1mg，硝酸钴和乙酸锌的总摩尔量与氧化石墨烯的投料配比为1×10-3mol:10mg，硝酸钴与乙酸锌的摩尔比为1:3-3:1，泡沫镍基底的尺寸为1cm×1cm×0.1cm。
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