CN109036864B - 一种纳米硫化镍-石墨烯复合电极材料的制备方法及应用 - Google Patents
一种纳米硫化镍-石墨烯复合电极材料的制备方法及应用 Download PDFInfo
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Abstract
本发明公开了一种纳米硫化镍‑石墨烯复合电极材料的制备方法及应用,属于电化学领域。本发明材料是通过将氧化石墨烯负载在碳纤维布上,再通过恒电位沉积法,将纳米氢氧化镍沉积在氧化石墨烯/碳纤维布表面的同时将氧化石墨烯还原,得到氢氧化镍‑石墨烯复合材料,最后与硫化钠反应,得到纳米硫化镍‑石墨烯复合材料。本发明的主要用在电化学储能和电化学传感器领域。
Description
技术领域
本发明属于电化学技术领域,更具体地是,涉及一种纳米硫化镍-石墨烯复合电极材料的制备方法及应用。
背景技术
随着材料科学和纳米技术的快速发展和相互融合,新型纳米复合材料的设计已成为电催化、电化学能量储存转换和电化学传感器等众多电化学领域的研究热点。石墨烯作为纳米碳材料家族中一颗耀眼的新星,其电子迁移率比硅高140倍、拉伸强度比相同厚度合金钢高100倍、面电阻比铜或银更低、生物相容性好、合成成本低廉且热力学稳定性高,这一系列优异的特性使其在电化学领域得到了广泛的应用。
为了满足实际应用需求,将石墨烯与过渡金属化合物进行复合是一种行之有效的方法,基于二者的协同作用能够得到最优异的电化学性能。如有人制备了四氧化三钴/石墨烯泡沫电极用于构筑超级电容器和无酶型葡萄糖传感器。硫化镍作为常见的过渡金属硫化物,具有独特的物理和化学性质,是目前具有较好的研究前景的电极材料。而具有纳米结构的硫化镍,如纳米线、纳米花、纳米片、纳米棒和纳米颗粒能赋予其较高的比表面积,有利于极大限度地提升电化学活性。
目前制备纳米硫化镍复合材料仍以水热或溶剂热法为主,中国专利201410373804.6报道了采用溶剂热法制备出硫化镍纳米颗粒,先通过表面活性剂对硫化镍颗粒表面改性,再与氧化石墨烯在静电吸引作用下复合;再采用水合肼将氧化石墨烯还原,最终形成石墨烯封装的纳米硫化镍/石墨烯复合正极材料。该制备方法采用表面活性剂后经热处理改性硫化镍的形貌,此制备方法过程可控性差且较复杂,很难得到纯度较高的硫化镍,对复合材料的电化学性能有影响。同时制备过程中采用有毒有机物水合肼为还原剂,具有一定危险性。该材料制备的电极只能在低电流密度下使用,且电化学性能不佳。因此采用新颖简单地方法制备出高效、双功能的纳米硫化镍复合材料,仍然是被业界广为研究却尚未解决的技术难题。
发明内容
针对现有的纳米硫化镍复合材料技术缺陷或改进需求,本发明提供了一种纳米硫化镍-石墨烯复合材料及其制备方法,目的在于解决目前硫化镍复合材料制备繁琐、性能单一的技术问题。
本发明提供了一种纳米硫化镍-石墨烯复合材料的制备方法,材料由石墨烯/导电基底和纳米硫化镍表层构成,制备步骤如下:(1)将导电基底材料置于氧化石墨烯溶液中,待表面负载完全,取出干燥。(2)以步骤(1)中制得氧化石墨烯/导电基底材料为工作电极,镍元素的盐溶液为电解液,采用恒电位沉积法,在一定电位及时间下将纳米氢氧化镍沉积在氧化石墨烯/导电基底表面的同时将氧化石墨烯还原,得到氢氧化镍-石墨烯复合材料。(3)将氢氧化镍-石墨烯复合材料与硫化钠反应,得到纳米硫化镍-石墨烯复合材料。
所述的制备方法步骤(1)中导电基底材料为碳纤维布,其规格为1cm*1cm,氧化石墨烯溶液的浓度为2mg/ml~4mg/ml,干燥为真空干燥,干燥温度为50~70℃,干燥时间为6~10h。
所述的制备方法步骤(2)中氧化石墨烯/碳纤维布工作电极中氧化石墨烯的含量为1~2mg/cm2。
所述的制备方法步骤(2)中镍元素的盐溶液为氯化镍,硝酸镍和硫酸镍中的一种。
优选的,所述的制备方法步骤(2)中镍元素的盐溶液为氯化镍,浓度为20~40mmol/L。
所述的制备方法步骤(2)中电位范围为-1.2~-1V,时间为10~20min。
优选的,所述的制备方法步骤(2)中电位为-1.1V,时间为10min。
所述的制备方法步骤(3)中氢氧化镍-石墨烯复合材料的质量为5~10mg。
所述的制备方法步骤(3)中硫化钠的浓度为0.1~0.2mol/L。
上述制备方法所得的纳米硫化镍层具有三维网状片层结构。
本发明还提供了上述制备出的纳米硫化镍-石墨烯复合材料在电化学储能和电化学传感器领域的应用。
本发明直接以高效的碳纤维作为导电基底,通过恒电位沉积法,将纳米氢氧化镍沉积在氧化石墨烯/碳纤维表面的同时将氧化石墨烯还原,再通过与硫化钠反应得到的目标产物。本发明与现有技术相比,具有如下有益效果:
1.首先,本发明与水热法、溶剂热法、沉淀法制备硫化镍-石墨烯纳米复合材料相比,该制备方法步骤简单新颖,不含有毒有机溶剂,避免污染。
2.其次,本发明使用碳纤维布作为导电基体,不但厚度薄,还增强电极材料的导电性和承载强度。
3.再次,本发明采用恒电位沉积法,在合适的电位及时间下使氢氧化镍沉积在氧化石墨烯/碳纤维布表面的同时将氧化石墨烯还原,由于氧化石墨烯上众多的含氧基团,可为氢氧化镍的生长提供丰富的活性位点,从而也增加了后续硫化镍纳米颗粒的分散性及电化学活性,优于直接在石墨烯表面沉积氢氧化镍。此方法既简化了合成的步骤又带来较好的应用效果。
4.最后,本发明制备出的纳米硫化镍-石墨烯复合电极材料不仅在应用于电化学传感器领域进行检测痕量葡萄糖小分子时,具有较高的检测灵敏度,还可将本发明提供的纳米硫化镍-石墨烯复合材料应用于电化学储能领域,具有较高的比电容。
附图说明
图1是实施例1碳布表面负载石墨烯的平面扫描电镜SEM图
图2是实施例1纳米硫化镍的平面扫描电镜SEM图。
图3是实施例1提供的纳米硫化镍-石墨烯复合材料的充放电性能测试图。
图4是实施例1制备的纳米硫化镍-石墨烯复合材料的电化学传感性能图。
具体实施方式
实施例1
1.纳米硫化镍-石墨烯复合电极材料的制备
(1)将洁净的1cm*1cm碳纤维布置于3mg/ml氧化石墨烯溶液中,待碳布表面完全负载氧化石墨烯后,取出碳布60℃真空下干燥8h得到约含1.6mg/cm2氧化石墨烯的氧化石墨烯/碳纤维布;
(2)组装三电极体系,以步骤(1)中获得的氧化石墨烯/导电碳基为工作电极,以30mmol/L的氯化镍为电解液,采用恒电位沉积法,沉积电位为-1.1V,沉积时间为10min,将纳米氢氧化镍沉积在石墨烯/碳纤维布表面的同时实现氧化石墨烯的电还原,得到氢氧化镍-石墨烯复合材料;
(3)将步骤(2)中获得的8mg氢氧化镍-石墨烯复合材料与0.1mol/L硫化钠反应,得到纳米硫化镍-石墨烯复合材料。
图1给出了碳布表面负载氧化石墨烯的平面扫描电镜(SEM)图,可见氧化石墨烯呈现皱褶状,紧密地包覆在碳布表面。图2为纳米硫化镍的平面扫描电镜(SEM)图,可见硫化镍呈现三维网状片层结构,纳米片的厚度为10~15nm。
2.纳米硫化镍-石墨烯复合材料充放电性能测试
采用三电极体系进行电化学测试,以测试实施例1中纳米硫化镍-石墨烯复合材料的电化学储能性能。测试系统为CHI660D电化学工作站,在0~0.5V电位区间的范围内进行充放电试验,充电的电流密度分别为1、2、4、6、8A/g。由图3可以看出,在1、2、4、6和8A/g时纳米硫化镍-石墨烯复合材料的质量电容分别为668.2、526.5、485.9、435.2、404.9F/g。当电流密度为1A/g时纳米硫化镍-石墨烯复合材料的质量电容最佳。
3.纳米硫化镍-石墨烯复合材料作为无酶型葡萄糖传感器
组装三电极体系,工作电极为实施例1的纳米硫化镍-石墨烯复合材料,辅助电极为铂电极,参比电极为氧化汞电极,测试底液为0.1mol/L氢氧化钠溶液。由图4可以看出,随着葡萄糖浓度的增加,循环伏安曲线的峰电流逐渐增加,当加入4mmol/L葡萄糖时,峰电流增加了255.3μA,检测性能良好。
实施例2
1.纳米硫化镍-石墨烯复合电极材料的制备
(1)将洁净的1cm*1cm碳纤维布置于2mg/ml氧化石墨烯溶液中,待碳布表面完全负载氧化石墨烯后,取出碳布50℃真空下干燥10h得到约含1mg/cm2氧化石墨烯的氧化石墨烯/碳纤维布;
(2)组装三电极体系,以步骤(1)中获得的氧化石墨烯/导电碳基为工作电极,以20mmol/L的硝酸镍为电解液,采用恒电位沉积法,沉积电位为-1.0V,沉积时间为20min,将纳米氢氧化镍沉积在石墨烯/碳纤维布表面的同时实现氧化石墨烯的电还原,得到氢氧化镍-石墨烯复合材料;
(3)将步骤(2)中获得的5mg氢氧化镍-石墨烯复合材料与0.15mol/L硫化钠反应,得到纳米硫化镍-石墨烯复合材料。
2.纳米硫化镍-石墨烯复合材料充放电性能测试
采用三电极体系进行电化学测试,以测试实施例2纳米硫化镍-石墨烯复合材料的电化学储能性能。测试系统为CHI660D电化学工作站,在0~0.5V电位区间的范围内进行充放电试验,当电流密度为1A/g时,纳米硫化镍-石墨烯复合材料的最佳质量电容为633.6F/g。
3.纳米硫化镍-石墨烯复合材料作为无酶型葡萄糖传感器
组装三电极体系,工作电极为实施例2的纳米硫化镍-石墨烯复合材料,辅助电极为铂电极,参比电极为氧化汞电极,测试底液为0.1mol/L氢氧化钠溶液。随着葡萄糖浓度的增加,循环伏安曲线的峰电流逐渐增加,检测性能良好。
实施例3
1.纳米硫化镍-石墨烯复合电极材料的制备
(1)将洁净的1cm*1cm碳纤维布置于4mg/ml氧化石墨烯溶液中,待碳布表面完全负载氧化石墨烯后,取出碳布70℃真空下干燥6h得到约含2mg/cm2氧化石墨烯的氧化石墨烯/碳纤维布;
(2)组装三电极体系,以步骤(1)中获得的氧化石墨烯/导电碳基为工作电极,以40mmol/L的硫酸镍为电解液,采用恒电位沉积法,沉积电位为-1.2V,沉积时间为15min,将纳米氢氧化镍沉积在石墨烯/碳纤维布表面的同时实现氧化石墨烯的电还原,得到氢氧化镍-石墨烯复合材料;
(3)将步骤(2)中获得的10mg氢氧化镍-石墨烯复合材料与0.2mol/L硫化钠反应,得到纳米硫化镍-石墨烯复合材料。
2.纳米硫化镍-石墨烯复合材料充放电性能测试
采用三电极体系进行电化学测试,以测试实施例3的纳米硫化镍-石墨烯复合材料的电化学储能性能。测试系统为CHI660D电化学工作站,在0~0.5V电位区间的范围内进行充放电试验,当电流密度为1A/g时,纳米硫化镍-石墨烯复合材料的最佳质量电容为647.6F/g。
3.纳米硫化镍-石墨烯复合材料作为无酶型葡萄糖传感器
组装三电极体系,工作电极为实施例3的纳米硫化镍-石墨烯复合材料,辅助电极为铂电极,参比电极为氧化汞电极,测试底液为0.1mol/L氢氧化钠溶液。随着葡萄糖浓度的增加,循环伏安曲线的峰电流逐渐增加,检测性能良好。
以上示意性地对本发明及其实施方式进行了描述,该描述没有限制性,附图中所示的也只是本发明的实施方式之一,实际的结构并不局限于此。所以,如果本领域的普通技术人员受其启示,在不脱离本发明创造宗旨的情况下,不经创造性地设计出与该技术方案相似的结构方式及实施例,均应属于本发明的保护范围。
Claims (11)
1.一种纳米硫化镍-石墨烯复合电极材料的制备方法,其特征在于,所述材料的制备步骤如下:
(1)将导电基底材料置于氧化石墨烯溶液中,负载后取出干燥;
(2)以步骤(1)中制得的氧化石墨烯/导电基底材料为工作电极,镍元素的盐溶液为电解液,采用恒电位沉积法,电位范围为-1.2~-1V,将纳米氢氧化镍沉积在氧化石墨烯/导电碳基表面,同时将氧化石墨烯还原,得到氢氧化镍-石墨烯复合材料;
(3)将氢氧化镍-石墨烯复合材料与硫化钠反应,得到纳米硫化镍-石墨烯复合材料。
2.根据权利要求1所述的制备方法,其特征在于,所述的步骤(1)中导电基底材料为碳纤维布,规格为1cm*1cm。
3.根据权利要求1所述的制备方法,其特征在于,所述的步骤(1)中氧化石墨烯溶液的浓度为2mg/ml~4mg/ml,干燥为真空干燥,干燥温度为50~70℃,干燥时间为6~10h。
4.根据权利要求1所述的制备方法,其特征在于,所述的步骤(2)中氧化石墨烯/导电基底材料工作电极中氧化石墨烯的含量为1~2mg/cm2;镍元素的盐溶液为氯化镍,硝酸镍和硫酸镍中的一种。
5.根据权利要求4所述的制备方法,其特征在于,所述的镍元素的盐溶液为氯化镍,浓度为20~40mmol/L。
6.根据权利要求1所述的制备方法,其特征在于,所述的步骤(2)中时间为10~20min。
7.根据权利要求6所述的制备方法,其特征在于,所述的电位为-1.1V,时间为10min。
8.根据权利要求1所述的制备方法,其特征在于,所述的步骤(3)中氢氧化镍-石墨烯复合材料的质量为5~10mg。
9.根据权利要求1所述的制备方法,其特征在于,所述的步骤(3)中硫化钠的浓度为0.1~0.2mol/L。
10.根据权利要求1至9任一项所述的制备方法,其特征在于,所述的纳米硫化镍为三维网状片层结构。
11.一种根据权利要求1-10任一项所述的制备方法所得到的石墨烯复合电极材料的应用,其特征在于,将其用于电化学储能和电化学传感器领域。
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