CN105161313B - 一种钴酸镍/碳纳米管复合材料的制备方法 - Google Patents
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Abstract
一种钴酸镍/碳纳米管复合材料的制备方法,它涉及一种碳纳米管负载纳米颗粒钴酸镍的制备方法,包括步骤:将Ni(NO3)2·6H2O和Co(NO3)2·6H2O溶于二甘醇中,配制成含Ni2+/Co2+摩尔比为1:2的混合金属溶液A;将NaOH和碳纳米管溶于二甘醇中,超声分散形成溶液B;将所述溶液B逐滴加入到溶液A中得到混合溶液;将所述混合溶液在80℃下充分搅拌均匀,移入反应釜,置换CO2,置换之后将CO2的压强调到10MPa;将反应釜放进油浴锅中,设置搅拌速率为400r/min,温度为140~220℃,反应时间为4~10h;所得产物用乙醇和蒸馏水清洗至中性,离心分离,80℃烘干得到钴酸镍/碳纳米管复合材料。本发明方法对碳纳米管的结构几乎没有破坏、操作简单、环境友好、不需煅烧可在溶液中直接得到产物;所获得的钴酸镍/碳纳米管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
技术领域
本发明涉及复合材料领域,具体涉及一种碳纳米管负载纳米钴酸镍的制备方法。
背景技术
近年来,超级电容器因其具有高功率密度、充电短时间和循环寿命长等诸多优点,广泛用于通信,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。电极材料是影响超级电容器性能的关键因素,以RuO2等贵金属氧化物因其赝电容原理有较大的比电容值,但昂贵的价格和毒性限制了其商业化应用。一些廉价金属氧化物代替贵金属作为超级电容器电极材料成为研究热点。钴酸镍(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;CN103318978B; 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。因此,人们考虑将NiCo2O4与碳材料或导电聚合物进行复合来提高材料的导电性,以达到增强其电化学性能的目的(如CN103117389B; CN104143450A)。
碳纳米管(CNTs)具有特殊的一维中空的纳米结构,它主要由呈六边形排列的碳原子构成的单层或数层的同轴圆管构成,具有优良的耐热、耐腐蚀、耐冲击性能,而且传热和导电性能好,使其有制备大容量超级电容器的潜在优势。但CNTs单独作为超级电容器电极材料比电容值过低,一般只有40F/g。鉴于过渡氧化物和碳纳米管之间的互补性,通常考虑将其复合,使该复合产物既具有赝电容特性,又具有双电层特性,从而制备出具有高比电容、高导电率、循环充放电稳定的超级电容器电极材料。Leela等(Asymmetric FlexibleSupercapacitor Stack, Nonoscale Research Letters, 2008)利用溶胶凝胶法制备金属氧化物/多壁碳纳米管复合电极材料,表现出优异的电化学性能,但溶胶凝胶法加入表面活性剂,容易引入杂质,而且成本较高;Kuan等(Electrodeposition of Nickel and CobaltMixed Oxide/Carbon Nanotube Thin Films and Their Charge Storage Properties,J. Electorchem. soc., 2006)、Fan等(Preparation and capacitive properties ofcobalt-nickel oxides/carbon nanotube coposites,Electrochim. Acta. 2007)和Wen等(A three dimensional vertically aligned multiwall carbon nanotube-NiCo2O4core-shell structure for novel high-performance supercapacitors, J. Mater.Chem. A, 2014)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,该方法反应时间长,耗能高;中国专利(CN1315139C)提供了一种碳纳米管与过渡氧化物复合的途径,利用粘结剂把碳纳米管和过渡金属氧化物复合,粘结剂的加入会增加材料的内阻,不利于该复合材料作为超级电容器电极材料。
发明内容
本发明的目的是提供一种钴酸镍/碳纳米管复合纳米电极材料的制备方法,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,本发明提供一种钴酸镍/碳纳米管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溶于二甘醇中,配制成含Ni2+/Co2+摩尔比为1:2的混合金属溶液A;将NaOH和碳纳米管溶于二甘醇中,超声分散形成溶液B;将所述溶液B逐滴加入到溶液A中得到混合溶液;将所述混合溶液在80℃下充分搅拌均匀,移入反应釜,置换CO2,置换之后将CO2的压强调到10MPa;将反应釜放进油浴锅中,设置搅拌速率为400r/min,温度为140~220℃,反应时间为4~10h;所得产物用乙醇和蒸馏水清洗至中性,离心分离,80℃烘干得到钴酸镍/碳纳米管复合材料。
本发明优点:一、本发明没有用强氧化剂处理碳纳米管,对碳纳米管的结构几乎没有破坏;二、本发明操作简单、环境友好、不需煅烧可在溶液中直接得到产物;三、所获得的钴酸镍/碳纳米管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)分析本发明制备的钴酸镍/碳纳米管复合纳米材料的物相,采用投射电子显微镜(TEM)表征本发明制备的钴酸镍/碳纳米管复合纳米材料的微观结构,采用电化学工作站来测试本发明制备的钴酸镍/碳纳米管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钴酸镍/碳纳米管复合材料。
附图说明
图1是实施方式一制备的钴酸镍/碳纳米管复合材料的XRD曲线图,证实制备的钴酸镍/碳纳米管复合材料含有钴酸镍物相和碳纳米管物相。
图2是实施方式一制备的钴酸镍/碳纳米管复合材料的TEM图,通过图2可知本发明制备的钴酸镍/碳纳米管复合材料形成了钴酸镍包覆碳纳米管的结构。
图3是实施方式一制备的钴酸镍/碳纳米管复合材料的循环伏安曲线图,通过图3可知本发明制备的钴酸镍/碳纳米管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钴酸镍/碳纳米管复合材料的恒流充放电曲线图,通过图4可知本发明制备的钴酸镍/碳纳米管复合材料在电流密度为1A/g、2A/g、4A/g、10A/g下的比电容值分别问938.8F/g、880F/g、820.8F/g、720F/g。
图5是实施方式一制备的钴酸镍/碳纳米管复合材料的循环稳定性能图,通过图5可知本发明制备的钴酸镍/碳纳米管复合材料在10A/g电流密度下经过1000次循环仍保持97%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钴酸镍/碳纳米管复合纳米磁性材料的制备方法,具体是按以下步骤完成的:将1.5mmol Ni(NO3)2·6H2O和3mmol Co(NO3)2·6H2O溶于20ml的二甘醇中,80℃下搅拌至溶解,配制成含Ni2+/Co2+摩尔比为1:2的混合金属溶液A;将9mmol NaOH和30mg碳纳米管溶于40ml二甘醇中,80℃下超声分散30min,形成溶液B;将所述溶液B逐滴加入到溶液A中得到混合溶液;将所述混合溶液在80℃下充分搅拌均匀,移入反应釜,置换CO2,置换之后将CO2的压强调到10MPa;将反应釜放进油浴锅中,设置搅拌速率为400r/min,温度为200℃,反应时间为8h;所得产物用乙醇和蒸馏水清洗至中性,离心分离,80℃烘干得到钴酸镍/碳纳米管复合材料。
具体实施方式二:一种钴酸镍/碳纳米管复合纳米磁性材料的制备方法,具体是按以下步骤完成的:将1.5mmol Ni(NO3)2·6H2O和3mmol Co(NO3)2·6H2O溶于10ml的二甘醇中,80℃下搅拌至溶解,配制成含Ni2+/Co2+摩尔比为1:2的混合金属溶液A;将7mmol NaOH和30mg碳纳米管溶于20ml二甘醇中,80℃下超声分散30min,形成溶液B;将所述溶液B逐滴加入到溶液A中得到混合溶液;将所述混合溶液在80℃下充分搅拌均匀,移入反应釜,置换CO2,置换之后将CO2的压强调到10MPa;将反应釜放进油浴锅中,设置搅拌速率为400r/min,温度为200℃,反应时间为8h;所得产物用乙醇和蒸馏水清洗至中性,离心分离,80℃烘干得到钴酸镍/碳纳米管复合材料。
具体实施方式三:一种钴酸镍/碳纳米管复合纳米磁性材料的制备方法,具体是按以下步骤完成的:将1.5mmol Ni(NO3)2·6H2O和3mmol Co(NO3)2·6H2O溶于20ml的二甘醇中,80℃下搅拌至溶解,配制成含Ni2+/Co2+摩尔比为1:2的混合金属溶液A;将9mmol NaOH和60mg碳纳米管溶于40ml二甘醇中,80℃下超声分散30min,形成溶液B;将所述溶液B逐滴加入到溶液A中得到混合溶液;将所述混合溶液在80℃下充分搅拌均匀,移入反应釜,置换CO2,置换之后将CO2的压强调到10MPa;将反应釜放进油浴锅中,设置搅拌速率为400r/min,温度为200℃,反应时间为8h;所得产物用乙醇和蒸馏水清洗至中性,离心分离,80℃烘干得到钴酸镍/碳纳米管复合材料。
具体实施方式四:一种钴酸镍/碳纳米管复合纳米磁性材料的制备方法,具体是按以下步骤完成的:将1.5mmol Ni(NO3)2·6H2O和3mmol Co(NO3)2·6H2O溶于20ml的二甘醇中,80℃下搅拌至溶解,配制成含Ni2+/Co2+摩尔比为1:2的混合金属溶液A;将9mmol NaOH和60mg碳纳米管溶于40ml二甘醇中,80℃下超声分散30min,形成溶液B;将所述溶液B逐滴加入到溶液A中得到混合溶液;将所述混合溶液在80℃下充分搅拌均匀,移入反应釜,置换CO2,置换之后将CO2的压强调到10MPa;将反应釜放进油浴锅中,设置搅拌速率为400r/min,温度为140℃,反应时间为10h;所得产物用乙醇和蒸馏水清洗至中性,离心分离,80℃烘干得到钴酸镍/碳纳米管复合材料。
具体实施方式五:一种钴酸镍/碳纳米管复合纳米磁性材料的制备方法,具体是按以下步骤完成的:将1.5mmol Ni(NO3)2·6H2O和3mmol Co(NO3)2·6H2O溶于20ml的二甘醇中,80℃下搅拌至溶解,配制成含Ni2+/Co2+摩尔比为1:2的混合金属溶液A;将9mmol NaOH和60mg碳纳米管溶于40ml二甘醇中,80℃下超声分散30min,形成溶液B;将所述溶液B逐滴加入到溶液A中得到混合溶液;将所述混合溶液在80℃下充分搅拌均匀,移入反应釜,置换CO2,置换之后将CO2的压强调到10MPa;将反应釜放进油浴锅中,设置搅拌速率为400r/min,温度为220℃,反应时间为4h;所得产物用乙醇和蒸馏水清洗至中性,离心分离,80℃烘干得到钴酸镍/碳纳米管复合材料。
Claims (4)
1.一种钴酸镍/碳纳米管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溶于二甘醇中,配制成含Ni2+/Co2+摩尔比为1:2的混合金属溶液A;将NaOH和碳纳米管溶于二甘醇中,超声分散形成溶液B;将所述溶液B逐滴加入到溶液A中得到混合溶液;将所述混合溶液在80℃下充分搅拌均匀,移入反应釜,置换CO2,置换之后将CO2的压强调到10MPa;将反应釜放进油浴锅中,设置搅拌速率为400r/min,温度为140~220℃,反应时间为4~10h;所得产物用乙醇和蒸馏水清洗至中性,离心分离,80℃烘干得到钴酸镍/碳纳米管复合材料。
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,NaOH在所述溶液B中的浓度为0.1~1.0mol/L,NaOH与所述的混合金属溶液A中Ni2+和Co2+的总的物质的量的比为1.5~2:1。
4.根据权利要求1所述的制备方法,其特征在于,碳纳米管加入的量为钴酸镍理论重量的5~50%。
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CN110272036B (zh) * | 2019-05-13 | 2021-03-23 | 中山大学 | 一种磁性物质掺杂的多壁碳纳米管的制备方法及其制备的多壁碳纳米管 |
CN112599348B (zh) * | 2020-12-09 | 2022-03-22 | 中国计量大学 | 一种同轴磁纳米电缆的制备方法 |
CN113201747A (zh) * | 2021-03-26 | 2021-08-03 | 广州费舍尔人工智能技术有限公司 | 一种磷改性钴酸镍修饰碳纳米管电极催化剂 |
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