CN106683894A - 一种Co3O4多孔纳米片阵列的制备方法及其应用 - Google Patents
一种Co3O4多孔纳米片阵列的制备方法及其应用 Download PDFInfo
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
本发明公开了一种Co3O4多孔纳米片阵列的制备方法及其应用。该制备方法为步骤1，将碳纤维纸依次经过丙酮、去离子水、乙醇超声清洗后晾干，备用；步骤2，将六水合硝酸钴溶于无水乙醇中，配成摩尔浓度为0.5‑3.5mol/L硝酸钴乙醇溶液；步骤3，用滴管将硝酸钴乙醇溶液滴浸于步骤1中洗净的碳纤维纸后真空干燥，重复2‑6次，使得每平方厘米碳纤维纸滴浸硝酸钴的量为0.05‑0.2mmol；步骤4，将酸钴重结晶/碳纤维纸焙烧得生长于碳纤维纸基底的多孔Co3O4纳米片阵列。本发明所得Co3O4多孔纳米片阵列作为超级电容器的电极材料时具有高比电容、优异的倍率性能和电化学稳定性。
Description
技术领域
本发明属于超级电容器电极材料制备领域，具体涉及一种Co3O4多孔纳米片阵列的制备方法及其应用。
背景技术
超级电容器是介于传统电容器和电池之间兼具较高功率密度和能量密度的新型储能器件，它具有功率密度高、循环寿命长等优势。根据电荷存储机理不同，超级电容器可以分为双电层超级电容器和赝电容超级电容器。双电层超级电容器通过电极-电解液界面的离子吸附进行电荷存储，它采用的电极材料主要为高比表面积、高导电性的碳材料。赝电容超级电容器通过发生在电极上的法拉第反应进行电荷存储，它采用的电极材料包括过渡金属氧化物（RuO2、MnO2、Co3O4、NiO等）和导电聚合物（聚苯胺、聚吡咯）两类。过渡金属氧化物电极具有较碳材料电极高的能量密度，较导电聚合物电极高的稳定性，是一类有应用潜力的超级电容器电极材料。
氧化物材料做为超级电容器电极时存在两个限制其电容性能提高的因素：一是法拉第反应通常发生在材料表面，使材料利用率不高，导致比电容量远低于理论容量；二是过渡金属氧化物，除RuO2外，通常导电性较差，限制了倍率性能的提高。为提高电极材料的利用率，研究集中于多孔和纳米结构的制备，以增加电解质和电极活性材料的接触面积。为提高电极材料的导电性，通常将氧化物与高导电性碳材料进行复合；除此之外，在集流体（泡沫镍、碳纸等）上原位生长氧化物一维纳米线或二维纳米片，也是提高氧化物电极导电性的有效方法。将氧化物原位生长与集流体，可以使活性氧化物与集流体更好的接触，使电子快速由氧化物活性位向集流体转移，而不会像被压制在集流体上的粉体材料那样，电子在无序的粉体颗粒间的传导增大了电阻。另一方面，将氧化物原位生长于集流体可避免粉体材料在电极制备中需加入的导电性差的粘结剂，从而避免了电极中导电“死区”的出现。
Co3O4具有高理论电容量（3560F/g），较低的价格和环境友好性，是一种有应用前景的赝电容电极材料。近年来已有多篇将一维或二维Co3O4生长于集流体的报道，目前的制备方法主要为液相法，包括水热反应法（Meilin Liu, et al., Nano Lett., 2012, 12,321-325; Peng Chen, et al., ACS Nano, 2012, 6, 3206-3213.）和电沉积法（J. B.Wu, Electrochimica Acta, 2011, 56, 7163-7170; Xiong Wen (David) Lou, EnergyEnviron. Sci., 2012, 5, 7883-7887.）。水热法中，将硝酸钴、氯化钴等钴盐和尿素、氨水等碱溶于去离子水，加入氟化钠等辅助剂，在水热条件下90-120℃反应8-16h，得到生长于集流体的Co(CO3)0.35Cl0.2(OH)1.1·1.74H2O, Co2(OH)2(CO3)2等阵列。将其在300-400℃温度下煅烧2-4h，得到生长于集流体的Co3O4一维或二维阵列。电沉积法中，将硝酸钴、硫酸钴等钴盐水溶液中加入硝酸钠、硫酸钠等辅助剂，在恒电流或恒电位下将Co(OH)2纳米片沉积于泡沫镍等集流体，然后在250-300℃煅烧2-4h得到Co3O4纳米片阵列。
以上两种液相法操作较为复杂，钴盐需在水热或电沉积条件下转化为Co2(OH)2(CO3)2或Co(OH)2等前驱体，再经煅烧步骤才可得到Co3O4。因此，寻求低成本、方法简单的生长于集流体的Co3O4阵列对于其产业化发展十分必要。
发明内容
针对现有技术的不足，本发明的目的在于提供一种Co3O4多孔纳米片阵列的制备方法及其应用，该方法操作简便，成本低廉，用本发明材料中制备的电极具有较高的比电容、优异的倍率性能和电化学稳定性。
为解决现有技术问题，本发明采取的技术方案为：
一种Co3O4多孔纳米片阵列的制备方法，包括以下步骤：
步骤1，将碳纤维纸依次经过丙酮、去离子水、乙醇超声清洗后晾干，备用；步骤2，将六水合硝酸钴溶于无水乙醇中，配成摩尔浓度为0.5-3.5mol/L硝酸钴乙醇溶液；
步骤3，用滴管将硝酸钴乙醇溶液滴浸于步骤1中洗净的碳纤维纸后真空干燥得重结晶硝酸钴/碳纤维纸，重复2-6次，使得每平方厘米碳纤维纸滴浸硝酸钴的量为0.05-0.2mmol；
步骤4，将重结晶硝酸钴/碳纤维纸焙烧得生长于碳纤维纸基底的多孔Co3O4纳米片阵列。
作为改进的是，步骤2中硝酸钴的浓度为2.0mol/L。
作为改进的是，步骤3中真空干燥温度为30-50℃，干燥时间为10-60min。
作为改进的是，步骤3中单位平方厘米碳纸所滴浸硝酸钴的量为0.18mmol。
作为改进的是，步骤4中焙烧的工艺条件为温度250-350℃，时间10-60min。
上述制备方法所得的Co3O4多孔纳米片阵列在超级电容器上的应用。
本发明将硝酸钴的乙醇溶液滴浸于碳纤维纸上，干燥过程中硝酸钴重结晶于碳纤维纸上，此时重结晶的硝酸钴表现为无规则形貌；焙烧首先使硝酸钴融化为液态并吸附于碳纤维上，随着焙烧温度继续升高硝酸钴分解为Co3O4，Co3O4原位结晶于碳纤维纸，并结晶为纳米片形貌；硝酸钴分解中产生的氮氧化物气体促成了Co3O4纳米片表面多孔结构的形成。所制备的电极由于活性Co3O4阵列直接生长于碳纸集流体，增加了电极导电性，此外，Co3O4多孔纳米片结构又提供了高活性面积和利于离子扩散的通道，从而提高了电极的储能性能。
有益效果
与现有技术相比，本发明具有两方面优势：
（1）本发明制备工艺简单，通过蒸发结晶将硝酸钴附着于碳纤维纸，不需要水热、电沉积等操作步骤，另外，所用原料只包括钴盐、乙醇，不需要其他辅助添加剂，成本低廉；
（2）本发明所制备的多孔Co3O4纳米片阵列具有优异的电化学性能，在1A/g充放电电流密度下电极的比电容达到842F/g，充放电电流密度增大到20A/g时比电容仍高达676F/g，循环充放电6000次后电极的比电容仍达到初始值的80%以上。
附图说明
图1是实施例1制备的Co3O4多孔纳米片阵列的SEM图片，（a）为低倍SEM，（b）为高倍SEM；
图2是实施例1制备的Co3O4多孔纳米片阵列的TEM图片；
图3是实施例1制备的Co3O4多孔纳米片阵列用于超级电容器电极时在不同电流密度下的充放电曲线；
图4是实施例1制备的Co3O4多孔纳米片阵列用于超级电容器电极时在不同充放电电流密度下的比电容；
图5是实施例1制备的Co3O4多孔纳米片阵列用于超级电容器电极时在电流密度4A/g下的循环稳定性曲线;
图6是本发明方法制备得致密Co3O4包覆碳纤维纸的SEM图片；
图7是在电流密度2A/g下致密Co3O4包覆碳纤维纸电极与Co3O4纳米片阵列制备得电极的充放电曲线对比。
具体实施方式
下面结合附图详细说明本发明的优选技术方案。
实施例1
一种Co3O4多孔纳米片阵列的制备方法，包括以下步骤：步骤1，将碳纤维纸切割成1×4cm的长条，依次经过丙酮、去离子水、乙醇中超声洗涤干净后备用；
步骤2，将5.8gCo(NO3)2·6H2O在超声辅助下溶解于10mL无水乙醇中，配制成2mol/L的硝酸钴乙醇溶液；
步骤3，用滴管取硝酸钴溶液0.1mL滴浸于碳纸，将其置于真空干燥箱中30℃干燥30min，继续取0.1mL硝酸钴溶液滴浸于干燥后的硝酸钴/碳纸，再次真空干燥；
步骤4，将蒸发结晶后的硝酸钴/碳纸置于马弗炉中焙烧，焙烧温度为300℃，时间10min, 得生长于碳纤维纸基底的多孔Co3O4纳米片阵列。
实施例2
一种Co3O4多孔纳米片阵列的制备方法，包括以下步骤：步骤1，将碳纤维纸切割成1×4cm的长条，依次经过丙酮、去离子水、乙醇中超声洗涤干净后备用；
步骤2，将2.9gCo(NO3)2·6H2O在超声辅助下溶解于10mL无水乙醇中，配制成1mol/L的硝酸钴乙醇溶液；
步骤3，用滴管取硝酸钴溶液0.1mL滴浸于碳纸，置于真空干燥箱中50℃干燥15min，继续取0.1mL硝酸钴溶液滴浸于干燥后的硝酸钴/碳纸，再次真空干燥；
步骤4，将蒸发结晶后的硝酸钴/碳纸置于管式炉中在氮气气氛下焙烧，焙烧温度为250℃，时间30min, 得生长于碳纤维纸基底的多孔Co3O4纳米片阵列。
性能测试
将实施例1制备得生长于碳纤维纸基底的多孔Co3O4纳米片阵列应用于超级电容器上作为电极材料，然后测定所得电容器的相关参数，如图3-5所示。
从图3-5的结果中可以看出，本发明生长于碳纤维纸基底的多孔Co3O4纳米片阵列应用于超级电容器上作为电极材料，在1A/g充放电电流密度下电极的比电容达到842F/g，充放电电流密度增大到20A/g时比电容仍高达676F/g，循环充放电6000次后电极的比电容仍达到初始值的80%以上
相同制备方法下制备了致密Co3O4包覆碳纤维纸电极，如图6所示。将此方法制备的Co3O4包覆碳纤维纸电极与 实施例1制备的生长于碳纤维纸基底的多孔Co3O4纳米片阵列应用于超级电容器上作为电极材料进行比较，从图7中可知， 2A/g恒电流充放电电流密度下两者的充放电曲线，可见纳米片阵列Co3O4的比电容远高于致密Co3O4，显示了纳米片阵列结构的电容存储优势。
以上所述，仅为本申请较佳的具体实施方式，但本申请的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本申请的保护范围之内。因此，本申请的保护范围应该以权利要求的保护范围为准。
Claims (6)
1.一种Co3O4多孔纳米片阵列的制备方法，其特征在于，包括以下步骤：
步骤1，将碳纤维纸依次经过丙酮、去离子水、乙醇超声清洗后晾干，备用；
步骤2，将六水合硝酸钴溶于无水乙醇中，配成摩尔浓度为0.5-3.5mol/L硝酸钴乙醇溶液；
步骤3，用滴管将硝酸钴乙醇溶液滴浸于步骤1中洗净的碳纤维纸后真空干燥得重结晶硝酸钴/碳纤维纸，重复2-6次，使得每平方厘米碳纤维纸滴浸硝酸钴的量为0.05-0.2mmol；
步骤4，将重结晶硝酸钴/碳纤维纸焙烧得生长于碳纤维纸基底的多孔Co3O4纳米片阵列。
2.根据权利要求1所述的一种Co3O4多孔纳米片阵列的制备方法，其特征在于，步骤2中硝酸钴的浓度为2.0mol/L。
3.根据权利要求1所述的一种Co3O4多孔纳米片阵列的制备方法，其特征在于，步骤3中真空干燥温度为30-50℃，干燥时间为10-60min。
4.根据权利要求1所述的一种Co3O4多孔纳米片阵列的制备方法，其特征在于，步骤3中单位平方厘米碳纸所滴浸硝酸钴的量为0.18mmol。
5.根据权利要求1所述的一种Co3O4多孔纳米片阵列的制备方法，其特征在于，步骤4中焙烧的工艺条件为温度250-350℃，时间10-60min。
6.基于根据权利要求1所述的一种Co3O4多孔纳米片阵列的制备方法所得的Co3O4多孔纳米片阵列在超级电容器上的应用。
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