CN106710891A - 一种NiCo2O4/活性炭复合材料的制备方法 - Google Patents

一种NiCo2O4/活性炭复合材料的制备方法 Download PDF

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CN106710891A
CN106710891A CN201710064548.6A CN201710064548A CN106710891A CN 106710891 A CN106710891 A CN 106710891A CN 201710064548 A CN201710064548 A CN 201710064548A CN 106710891 A CN106710891 A CN 106710891A
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徐靖才
洪波
彭晓领
王新庆
李静
金红晓
金顶峰
杨艳婷
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Abstract

一种NiCo2O4/活性炭复合材料的制备方法，它涉及一种NiCo2O4纳米片负载活性炭的制备方法，包括步骤：将Ni(NO3)2·6H2O和 Co(NO3)2·6H2O溶于蒸馏水中，配制成含Ni2+/Co2+摩尔比为1:2的金属溶液，然后加入一定量的活性炭，搅拌均匀后逐滴加入氨水调节pH值，移入反应釜中100~200℃反应8~16h；所得产物用乙醇和蒸馏水清洗至中性，离心分离，100℃烘干得到复合材料前驱体；将前驱体在300℃煅烧2h得到NiCo2O4/活性炭复合材料。本发明方法具有操作简单、环境友好、耗能低等优点；所获得的NiCo2O4/活性炭复合材料用于超级电容器电极时具有较高的比电容值和良好的电化学性能稳定性。

Description

一种NiCo2O4/活性炭复合材料的制备方法
技术领域
本发明涉及复合材料领域，具体涉及一种NiCo2O4纳米片负载活性炭的制备方法。
背景技术
近年来，超级电容器因其高功率密度、快速充电功能、良好的循环稳定性和长循环寿命，广泛应用于通信，航空航天，大型工业装备，微电子器件等诸多等要求瞬间释放超大电流的场合，尤其是在新能源汽车领域有着广阔的应用前景。根据能量存储机制，超级电容器可以分为双电层电容和赝电容两种类型。双电层电容的电极材料主要是碳基材料，包括活性炭、碳纤维、碳纳米管、石墨烯等，它们依靠碳材料双电层静电场储存能量；赝电容的电极材料主要是金属氧化物材料，主要依靠它们快速、可逆的氧化还原反应储存能量。NiCo2O4是一种典型的尖晶石结构复合金属氧化物，存在Co3+/Co2+及Ni3+/Ni2+氧化还原电对，可以获得较高的工作电压窗口和比电容值，同时因其廉价无毒表现为极具潜力的电极材料，因此不同结构、形态、尺寸的NiCo2O4的制备受到了众多研究人员的关注（如CN102259936B;CN102092797B; CN102745752A; CN103107025A; CN103594246A; CN104003455B;CN104659358A）。然而与贵金属氧化物相比，NiCo2O4由于其导电性较差，导致比电容偏低，在大电流密度下充循环冲放电不够稳定。因而，需要以一定的方式将NiCo2O4和碳材料复合，来提高电极材料的导电性，以达到增强其电化学性能的目的。如Wen等利用电化学沉积方法制备了钴镍氧化物/碳纳米管复合材料（J. Mater. Chem. A, 2014, 2, 5100）; 谢健等利用一步低温法发明了一种镍钴氧化物/石墨烯复合材料（CN103117389B）。然而，尽管碳纳米管和石墨烯结合NiCo2O4复合材料具有较高的导电性和优异的超级电容性能，但这些碳纳米材料制备困难、价格昂贵，难以商业化大规模生产。而活性炭原料范围广、制备成本低，且具有高比表面积、高导电性和良好的吸附性能等优点。将活性炭与NiCo2O4组成复合电极材料，两者可以取长补短，有望得到具有高比电容、高导电率、循环充放电稳定的超级电容器电极材料。
发明内容
本发明的目的是提供一种NiCo2O4/活性炭复合材料的制备方法，该方法可以提高超级电容器电极材料的比电容和循环充放电稳定性。
为了实现上述目的，本发明提供一种NiCo2O4/活性炭复合材料的制备方法，其特征在于，具体包括以下步骤：将Ni(NO3)2·6H2O和 Co(NO3)2·6H2O溶于蒸馏水中，配制成含Ni2 +/Co2+摩尔比为1:2的金属溶液，然后加入一定量的活性炭，搅拌均匀后逐滴加入氨水调节pH值，移入反应釜中100~200℃反应8~16h；所得产物用乙醇和蒸馏水清洗至中性，离心分离，100℃烘干得到复合材料前驱体；将前驱体在300℃煅烧2h得到NiCo2O4/活性炭复合材料。
本发明优点：本发明方法具有操作简单、环境友好、耗能低等优点；所获得的NiCo2O4/活性炭复合材料用于超级电容器电极时具有较高的比电容值和良好的电化学性能稳定性。
本发明采用X射线衍射技术（XRD）分析本发明制备的NiCo2O4/活性炭复合材料的物相，采用扫描电子显微镜（SEM）表征本发明制备的NiCo2O4/活性炭复合材料的微观结构，采用电化学工作站来测试本发明制备的NiCo2O4/活性炭复合材料的电化学性能，可知本发明成功制备出了具有较高的比电容值和良好的电化学性能稳定性的NiCo2O4/活性炭复合材料。
附图说明
图1是实施方式一制备的NiCo2O4/活性炭复合材料的XRD曲线图，证实制备的NiCo2O4/活性炭复合材料含有NiCo2O4物相和活性炭物相。
图2是实施方式一制备的NiCo2O4/活性炭复合材料的SEM图，通过图2可知本发明制备的NiCo2O4/活性炭复合材料形成了NiCo2O4纳米片负载活性炭的结构。
图3是实施方式一制备的NiCo2O4/活性炭复合材料的循环伏安曲线图，通过图3可知本发明制备的NiCo2O4/活性炭复合材料表现出良好的循环伏安特性和Co3+/Co2+及Ni3+/Ni2+氧化还原峰。
图4是实施方式一制备的NiCo2O4/活性炭复合材料的恒流放电曲线图，通过图4可知本发明制备的NiCo2O4/活性炭复合材料在电流密度为1 A/g、2 A/g、4 A/g、8 A/g、16 A/g下的比电容值分别为273.5 F/g, 234.5 F/g, 208 F/g, 180 F/g, 152 F/g。
图5是实施方式一制备的NiCo2O4/活性炭复合材料的循环稳定性能图，通过图5可知本发明制备的NiCo2O4/活性炭复合材料在1 A/g电流密度下经过3000次循环仍保持96%以上的比电容值，在16 A/g电流密度下经过2500次循环仍保持80%以上的比电容值。
具体实施方式
下面是结合具体实施例，进一步阐述本发明。这些实施例仅用于说明本发明，但不用来限制本发明的范围。
具体实施方式一：一种NiCo2O4/活性炭复合材料的制备方法，具体是按以下步骤完成的：将5 mmol Ni(NO3)2·6H2O和10 mmol Co(NO3)2·6H2O溶于60 ml的蒸馏水中，配制成含Ni2+/Co2+摩尔比为1:2的混合金属溶液A；然后加入4.8 g活性炭，搅拌均匀后逐滴加入氨水调节pH=10，移入反应釜中180℃反应12 h；所得产物用乙醇和蒸馏水清洗至中性，离心分离，100℃烘干得到复合材料前驱体；将前驱体在300℃煅烧2h得到NiCo2O4/活性炭复合材料。
具体实施方式二：一种NiCo2O4/活性炭复合材料的制备方法，具体是按以下步骤完成的：将5 mmol Ni(NO3)2·6H2O和10 mmol Co(NO3)2·6H2O溶于60 ml的蒸馏水中，配制成含Ni2+/Co2+摩尔比为1:2的混合金属溶液A；然后加入1.2 g活性炭，搅拌均匀后逐滴加入氨水调节pH=10，移入反应釜中180℃反应12 h；所得产物用乙醇和蒸馏水清洗至中性，离心分离，100℃烘干得到复合材料前驱体；将前驱体在300℃煅烧2h得到NiCo2O4/活性炭复合材料。
具体实施方式三：一种NiCo2O4/活性炭复合材料的制备方法，具体是按以下步骤完成的：将5 mmol Ni(NO3)2·6H2O和10 mmol Co(NO3)2·6H2O溶于60 ml的蒸馏水中，配制成含Ni2+/Co2+摩尔比为1:2的混合金属溶液A；然后加入4.8 g活性炭，搅拌均匀后逐滴加入氨水调节pH=10，移入反应釜中100℃反应18 h；所得产物用乙醇和蒸馏水清洗至中性，离心分离，100℃烘干得到复合材料前驱体；将前驱体在300℃煅烧2h得到NiCo2O4/活性炭复合材料。
具体实施方式四：一种NiCo2O4/活性炭复合材料的制备方法，具体是按以下步骤完成的：将5 mmol Ni(NO3)2·6H2O和10 mmol Co(NO3)2·6H2O溶于60 ml的蒸馏水中，配制成含Ni2+/Co2+摩尔比为1:2的混合金属溶液A；然后加入6.0 g活性炭，搅拌均匀后逐滴加入氨水调节pH=7，移入反应釜中200℃反应6 h；所得产物用乙醇和蒸馏水清洗至中性，离心分离，100℃烘干得到复合材料前驱体；将前驱体在300℃煅烧2h得到NiCo2O4/活性炭复合材料。
具体实施方式五：一种NiCo2O4/活性炭复合材料的制备方法，具体是按以下步骤完成的：将5 mmol Ni(NO3)2·6H2O和10 mmol Co(NO3)2·6H2O溶于60 ml的蒸馏水中，配制成含Ni2+/Co2+摩尔比为1:2的混合金属溶液A；然后加入4.8 g活性炭，搅拌均匀后逐滴加入氨水调节pH=10，移入反应釜中140℃反应16 h；所得产物用乙醇和蒸馏水清洗至中性，离心分离，100℃烘干得到复合材料前驱体；将前驱体在300℃煅烧2h得到NiCo2O4/活性炭复合材料。
具体实施方式六：一种NiCo2O4/活性炭复合材料的制备方法，具体是按以下步骤完成的：将5 mmol Ni(NO3)2·6H2O和10 mmol Co(NO3)2·6H2O溶于60 ml的蒸馏水中，配制成含Ni2+/Co2+摩尔比为1:2的混合金属溶液A；然后加入2.4 g活性炭，搅拌均匀后逐滴加入氨水调节pH=12，移入反应釜中180℃反应18 h；所得产物用乙醇和蒸馏水清洗至中性，离心分离，100℃烘干得到复合材料前驱体；将前驱体在300℃煅烧2h得到NiCo2O4/活性炭复合材料。
具体实施方式七：一种NiCo2O4/活性炭复合材料的制备方法，具体是按以下步骤完成的：将5 mmol Ni(NO3)2·6H2O和10 mmol Co(NO3)2·6H2O溶于60 ml的蒸馏水中，配制成含Ni2+/Co2+摩尔比为1:2的混合金属溶液A；然后加入4.8 g活性炭，搅拌均匀后逐滴加入氨水调节pH=10，移入反应釜中200℃反应10 h；所得产物用乙醇和蒸馏水清洗至中性，离心分离，100℃烘干得到复合材料前驱体；将前驱体在300℃煅烧2h得到NiCo2O4/活性炭复合材料。

Claims (3)

1.一种NiCo2O4/活性炭复合材料的制备方法，其特征在于，由以下步骤组成：将Ni(NO3)2·6H2O和 Co(NO3)2·6H2O溶于蒸馏水中，配制成含Ni2+/Co2+摩尔比为1:2的金属溶液A，然后加入一定量的活性炭，搅拌均匀后逐滴加入氨水调节pH值，移入反应釜中100~200℃反应8~16h；所得产物用乙醇和蒸馏水清洗至中性，离心分离，100℃烘干得到复合材料前驱体；将前驱体在300℃煅烧2h得到NiCo2O4/活性炭复合材料。
2.根据权利要求1所述的制备方法，其特征在于，所述的混合金属溶液A中，Ni2+和Co2+的总浓度为0.1~1.0mol/L。
3.根据权利要求1所述的制备方法，其特征在于，NiCo2O4加入的量为活性炭理论重量的5~50%。
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WO2020244186A1 (zh) * 2019-06-06 2020-12-10 宁波中车新能源科技有限公司 一种超级电容器用活性炭及其制备方法和应用

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