CN108155028B - 一种类花状二硫化钼高性能超级电容器电极的制备方法 - Google Patents
一种类花状二硫化钼高性能超级电容器电极的制备方法 Download PDFInfo
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Abstract
本发明公开了一种类花状二硫化钼高性能超级电容器电极的制备方法,其是首先通过两步水热法合成不同尺寸大小的类花状MoS2纳米球,然后将其作为活性物质与导电物质、粘合剂混合制得高比电容的电极。本发明所得电极比电容可达到932F g‑1,是目前基于此材料在相同测试条件下公开报道的最高值,且电极在1000次恒流充放电后比电容的保持率仍可达到78%。
Description
技术领域
本发明属于以金属硫化物作为电极材料的超级电容器制备方法技术领域,具体涉及到应用于超级电容器的类花状二硫化钼电极材料的制备。
背景技术
超级电容器作为一种新型储能装置,具有比传统电容器高的能量密度和比电容、比电池高的功率密度、对环境污染小等优点,因而有着广阔的应用前景。发展超级电容器最有效的方式就是研发出具有优越性能的电极材料。二硫化钼(MoS2)作为典型的金属硫化物,由于其比氧化物高的内在离子电导率、比石墨高的理论比电容和类石墨烯的层状结构,从而广泛用于超级电容器电极材料,近年来倍受科学家们的关注。例如,small期刊2013年第2905页Cao等报道了使用可涂覆的MoS2纳米薄膜制作微型超级电容器,结果表明二硫化钼在水性电解质中具有优异的电化学性能。另外在电化学学报(Electrochimica Acta)2014年第397页Ke-Jing Huang等报道了用水热法合成MoS2纳米片,其在1A/g的电流密度下比电容达到129.2F/g、500次循环充放电之后有85.1%的电容保持率,虽此报导方法在循环稳定性上有良好表现,但是比电容太低。又见英国皇家化学会期刊(RSC Advances)2016年第6卷第39159页Swapnil S.Karade等报道了用水浴沉积法(CBD)在硅片基底上生长出MoS2纳米薄片,其在5mV/s的扫描速率下比电容达到576F/g,此方法制备的MoS2电极材料比电容有了很大提高,但产量不高。
总之,现有MoS2纳米结构应用于超级电容器电极的报导都充分说明MoS2是一种拥有潜在应用价值的超级电容器电极材料。核心问题是如何设计、制备出具有特殊结构的MoS2纳米材料以提高超级电容器电极性能,尤其是比电容和能量密度等性能。已报导的方法还存在不足,亟需优化提高。
发明内容
为解决上述现有技术所存在的不足之处,本发明提供了一种类花状二硫化钼高性能超级电容器电极的制备方法,所得电极具有极高的比电容和优异的电容保持率。
本发明为实现发明目的,采用如下技术方案:
本发明类花状二硫化钼高性能超级电容器电极的制备方法,其特点在于,包括如下步骤:
(1)将钼片与硫脲、硝酸混合置于不锈钢反应釜内衬中密封,200℃反应24小时;反应结束后自然冷却至室温,所得产物用乙醇和蒸馏水清洗,最后真空干燥,得到中间产物MoO3;
(2)取中间产物MoO3和硫脲溶于蒸馏水中,磁力搅拌均匀,然后转移至不锈钢反应釜内衬中密封,160~240℃反应24小时,反应结束后自然冷却至室温,所得产物用离心机离心分离,再用乙醇和蒸馏水清洗,最后真空干燥,得到类花状MoS2纳米球;
(3)将类花状MoS2纳米球与炭黑、聚偏二氟乙烯按照质量比(8~10):1:1的比例混合溶于N-甲基吡咯烷酮中,搅拌均匀,所得混合物涂覆于泡沫镍上,然后在15~25MPa的压力下对泡沫镍进行压片处理,最后置于真空干燥箱中70~100℃保持6~12小时,即获得类花状二硫化钼高性能超级电容器电极。
优选的,步骤(1)中,钼片与硫脲的摩尔比为1:1,所述硝酸的质量浓度为65%~68%,钼片与硝酸的质量体积比为1g:30mL。
优选的,步骤(2)中,所述中间产物和硫脲的摩尔比为1:7.5。
优选的,步骤(2)中,所述磁力搅拌的时间为90分钟,所述离心机离心的转速为8000r/min。
优选的,步骤(3)中,类花状MoS2纳米球与炭黑、聚偏二氟乙烯的质量比为8:1:1。
优选的,步骤(3)中,压片压力为20兆帕,真空干燥箱温度为90℃。
本发明的有益效果体现在:
1、本发明方法制备的MoS2电极,在电流密度为2A g-1时,比电容性能高达932F g-1,是目前基于此材料在相同测试条件下公开报道的最高值;且电极在7Ag-1的电流密度下充放电1000次后,电容保持率为78%,比电容性能优异;
2、本发明以合成的中间产物MoO3为钼源,替代了目前用过的钼酸铵、钼酸钠、硫代钼酸铵等,以硫脲为硫源,无需添加其他还原剂即可得到类花状MoS2纳米球。
3、本发明工艺操作简单、制备效率高,整个过程能耗低、无污染,对环境友好,且所用试剂价格低廉、环保。
附图说明
图1为实施例1所得类花状MoS2纳米球的扫描电镜图;
图2为实施例1、2、3中160℃、200℃、240℃条件下所得类花状MoS2纳米球的XRD衍射图谱;
图3为实施例1所得MoS2电极片在特定的电流密度下的恒流充放电图;
图4为实施例2所得类花状MoS2纳米球的扫描电镜照片;
图5为实施例2所得类花状MoS2纳米球的低倍透射电镜图。
图6为实施例2所得类花状MoS2纳米球的高倍透射电镜图;
图7为实施例2所得类花状MoS2纳米球的X射线光电子能谱分析图谱;
图8为实施例2所得MoS2电极片在特定的电流密度下的恒流充放电图;
图9为实施例3所得类花状MoS2纳米球的扫描电镜照片;
图10为实施例3所得MoS2电极片在特定的电流密度下的恒流充放电图;
图11为实施例3所得MoS2电极片在7A g-1电流密度下的恒流循环充放1000次的电容保持率图。
具体实施方式
下面结合附图对本发明的实施例作详细说明,下述实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1、160℃条件下MoS2电极的制备
(1)称取0.5g钼片(厚度为0.03mm)、0.4g硫脲粉末置于100mL聚四氟乙烯内衬的不锈钢反应釜中,再量取15mL质量浓度为68%的硝酸倒入反应釜内衬,高压密封;然后将反应釜放在200℃的高温炉中反应24小时;反应结束后自然冷却至室温,所得产物用乙醇和蒸馏水清洗,最后真空干燥,得到中间产物MoO3。
(2)取0.1536g中间产物MoO3和0.6113g硫脲加入装有40mL蒸馏水的烧杯中,室温下磁力搅拌60分钟,然后转移至100mL聚四氟乙烯内衬的不锈钢反应釜中密封,160℃反应24小时,反应结束后自然冷却至室温,所得产物用离心机离心分离(离心的转速为8000r/min),再用乙醇和蒸馏水各清洗4次,最后真空干燥,得到类花状MoS2纳米球。
(3)将类花状MoS2纳米球与炭黑、聚偏二氟乙烯按照质量比8:1:1的比例混合溶于N-甲基吡咯烷酮中,搅拌均匀,所得混合物涂覆于泡沫镍(泡沫镍的大小为1×1.5cm)上,然后在20MPa的压力下对泡沫镍进行压片处理,最后置于真空干燥箱中90℃保持12小时,即获得类花状MoS2电极片。
图1为本实施例所得类花状MoS2纳米球的扫描电镜照片,从图中可以看出MoS2呈现出纳米球状结构,分布均匀,且纳米球直径约为200nm。
图2底部那条XRD衍射峰谱线来自本实施例水热温度为160℃时制备所得的类花状MoS2纳米材料,其与2H-MoS2的标准衍射谱线(JCPDS:37-1492)的峰位对应,可以判断所制备的材料为2H-MoS2。
图3为本实施例所得电极片的比电容化学性质,从图中可以看出电流密度为2Ag-1时比电容达到488.5F g-1。
由上可见,采用本实施例的条件能够成功制备出分布均匀的类花状MoS2纳米球,160℃条件下制备的MoS2电极在电流密度为2Ag-1的恒流充放电下比电容可达到488.5F g-1。
实施例2、200℃条件下MoS2电极的制备
(1)称取0.5g钼片(厚度为0.03mm)、0.4g硫脲粉末置于100mL容积聚四氟乙烯内衬的不锈钢反应釜中,再量取15mL质量浓度为68%的硝酸倒入反应釜内衬,高压密封;然后将反应釜放在200℃的高温炉中反应24小时;反应结束后自然冷却至室温,所得产物用乙醇和蒸馏水清洗,最后真空干燥,得到中间产物MoO3。
(2)取0.1536g中间产物MoO3和0.6113g硫脲加入装有40mL蒸馏水的烧杯中,室温下磁力搅拌60分钟,然后转移至100mL聚四氟乙烯内衬的不锈钢反应釜中密封,200℃反应24小时,反应结束后自然冷却至室温,所得产物用离心机离心分离(离心的转速为8000r/min),再用乙醇和蒸馏水各清洗4次,最后真空干燥,得到类花状MoS2纳米球。
(3)将类花状MoS2纳米球与炭黑、聚偏二氟乙烯按照质量比8:1:1的比例混合溶于N-甲基吡咯烷酮中,搅拌均匀,所得混合物涂覆于泡沫镍(泡沫镍的大小为1×1.5cm)上,然后在20MPa的压力下对泡沫镍进行压片处理,最后置于真空干燥箱中90℃保持12小时,即获得类花状MoS2电极片。
图4为本实施例所得类花状MoS2纳米球的扫描电镜照片,从图中可以看出MoS2纳米球的直径约为200nm~300nm,且分布均匀。
图2中间那条XRD衍射峰谱线来自本实施例水热温度为200℃时制备所得的类花状MoS2纳米材料,其与2H-MoS2的标准衍射谱线(JCPDS:37-1492)的峰位对应,可以判断所制备的材料为2H-MoS2。
图5为本实施例所得类花状MoS2纳米球的低倍透射电镜图,从图中可以看出类花状MoS2的形貌特性。
图6为本实施例所得类花状MoS2纳米球的高倍透射电镜图,经过分析测量,其一晶面间距约为0.62nm与2H-MoS2(002)晶面间距完全符合。由此进一步证实了所制备的材料为2H-MoS2材料。
图7为本实施例所得类花状MoS2纳米球的X射线光电子能谱分析图谱,通过将图中各峰的位置比较,可以很清楚的确定样品表面Mo、S化学元素的存在。
图8为本实施例所得电极片的比电容化学性质,从图中可以看出电流密度为2Ag-1时比电容达到587.5F g-1。
由上可见,采用本实施例的条件能够成功制备出分布均匀且尺寸可调的类花状MoS2纳米球,200℃条件下制备的MoS2电极在电流密度为2Ag-1的恒流充放电下比电容可达到587.5Fg-1。
实施例3、240℃条件下MoS2电极的制备
(1)称取0.5g钼片(厚度为0.03mm)、0.4g硫脲粉末置于100mL容积聚四氟乙烯内衬的不锈钢反应釜中,再量取15mL质量浓度为68%的硝酸倒入反应釜内衬,高压密封;然后将反应釜放在200℃的高温炉中反应24小时;反应结束后自然冷却至室温,所得产物用乙醇和蒸馏水清洗,最后真空干燥,得到中间产物MoO3。
(2)取0.1536g中间产物MoO3和0.6113g硫脲加入装有40mL蒸馏水的烧杯中,室温下磁力搅拌60分钟,然后转移至100mL聚四氟乙烯内衬的不锈钢反应釜中密封,240℃反应24小时,反应结束后自然冷却至室温,所得产物用离心机离心分离(离心的转速为8000r/min),再用乙醇和蒸馏水各清洗4次,最后真空干燥,得到类花状MoS2纳米球。
(3)将类花状MoS2纳米球与炭黑、聚偏二氟乙烯按照质量比8:1:1的比例混合溶于N-甲基吡咯烷酮中,搅拌均匀,所得混合物涂覆于泡沫镍(泡沫镍的大小为1×1.5cm)上,然后在20MPa的压力下对泡沫镍进行压片处理,最后置于真空干燥箱中90℃保持12小时,即获得类花状MoS2电极片。
图9为本实施例所得类花状MoS2纳米球的扫描电镜照片,从图中可以看出MoS2纳米球的直径约为400nm~500nm,且分布均匀。
图2顶部那条XRD衍射峰谱线来自本实施例水热温度为240℃时制备所得的类花状MoS2纳米材料,其与2H-MoS2的标准衍射谱线(JCPDS:37-1492)的峰位对应,可以判断所制备的材料为2H-MoS2。
图10为本实施例所得电极片的比电容化学性质,从图中可以看出电流密度为2Ag-1时比电容达到932F g-1。
由上可见,采用本实施例的条件能够成功制备出分布均匀且尺寸可调的类花状MoS2纳米球,240℃条件下制备的MoS2电极在电流密度为2A g-1的恒流充放电下比电容可达到932F g-1。
图11为本实施例所得电极片在7A g-1电流密度下的恒流充放1000次循环充放电图。从该图可以看出在循环1000次后比电容保持率仍然可以达到78%。
以上仅为本发明的示例性实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (4)
1.一种类花状二硫化钼高性能超级电容器电极的制备方法,其特征在于,包括如下步骤:
(1)将钼片与硫脲、硝酸混合置于不锈钢反应釜内衬中密封,200℃反应24小时;反应结束后自然冷却至室温,所得产物用乙醇和蒸馏水清洗,最后真空干燥,得到中间产物MoO3;
其中,钼片与硫脲的摩尔比为1:1,所述硝酸的质量浓度为65%~68%,钼片与硝酸的质量体积比为1g:30mL;
(2)取中间产物MoO3和硫脲按摩尔比为1:7.5溶于蒸馏水中,磁力搅拌均匀,然后转移至不锈钢反应釜内衬中密封,160~240℃反应24小时,反应结束后自然冷却至室温,所得产物用离心机离心分离,再用乙醇和蒸馏水清洗,最后真空干燥,得到类花状MoS2纳米球;
(3)将类花状MoS2纳米球与炭黑、聚偏二氟乙烯按照质量比(8~10):1:1的比例混合溶于N-甲基吡咯烷酮中,搅拌均匀,所得混合物涂覆于泡沫镍上,然后在15~25MPa的压力下对泡沫镍进行压片处理,最后置于真空干燥箱中70~100℃保持6~12小时,即获得类花状二硫化钼高性能超级电容器电极。
2.根据权利要求1所述的类花状二硫化钼高性能超级电容器电极的制备方法,其特征在于,步骤(2)中,所述磁力搅拌的时间为60~90分钟,所述离心机离心的转速为8000r/min。
3.根据权利要求1所述的类花状二硫化钼高性能超级电容器电极的制备方法,其特征在于:步骤(3)中,类花状MoS2纳米球与炭黑、聚偏二氟乙烯的质量比为8:1:1。
4.根据权利要求1所述的类花状二硫化钼高性能超级电容器电极的制备方法,其特征在于:步骤(3)中,压片压力为20兆帕,真空干燥箱温度为90℃。
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