摘要
与添加反应前驱体合成元素掺杂纳米材料不同,本工作以盐酸预处理泡沫镍上形成的氯化镍为镍源,采用水热法在酸化预处理泡沫镍上合成了原位Ni掺杂CoMoO_(4)电极材料。通过调节水热反应温度(120、150、180、200℃)改变Ni掺杂CoMoO_(4)电极材料的形貌,进而控制其电容性能。随着水热反应温度的提高,Ni掺杂CoMoO_(4)的形貌由薄纳米片变为厚纳米片,同时比表面积也逐渐增大,在反应温度180℃达到最大值。水热温度180℃时在电流密度5mA·cm^(–2)下具有4680 mF·cm^(–2)的高比电容,120℃时在5 mA·cm^(–2)下比电容为1890 F·cm^(–2),而未掺杂的CoMoO_(4)纳米材料在5 mA·cm^(–2)下的比电容仅为1690mF·cm^(–2)。利用水热反应温度为180℃合成的Ni掺杂CoMoO_(4)与活性炭(AC)组装的非对称超级电容器(ASC),在10000次循环后的电容保持率为95%。通过原位Ni掺杂和调节水热反应温度改变Ni掺杂CoMoO_(4)的生长方式和微观形貌,显著改善了CoMoO_(4)的电容性能。
Introduction Energy,environment and industrial production are interconnected with the rapid development of the industrialization process,conventional fossil fuels are close to exhaustion,and the environment on which mankind depends for survival is seriously damaged.The development of efficient,clean and sustainable energy conversion and storage technology is thus an important research direction in scientific community.In this paper,in-situ Ni-doped CoMoO_(4) electrode materials were synthesized on acidified pretreated nickel foam with nickel chloride formed on hydrochloric acid pretreated nickel foam as a reactive nickel source.The capacitive properties of in-situ Ni-doped CoMoO_(4) electrode materials synthesized at different hydrothermal reaction temperatures were investigated. Methods In this work, 1 mmol Co(NO3)2·6H2O and 1 mmol Na2MoO_(4)·2H2O were dissolved in 60 mL of deionized water (DI) andstirred for 30 min, and then the conventionally cleaned nickel foams and four pieces of acidified pretreated nickel foams wereimmersed into five beakers of the solutions above, respectively. The solutions were then transferred into a hydrothermal high-pressurereactor lined with polytetrafluoroethylene. The reactor was kept in an oven at different temperatures (i.e.,180, 120, 150, 180 ℃, and200 ℃) for 12 h, respectively. The nickel foam was removed from the cooled reactor, washed and dried in a vacuum oven at 60 ℃for 12 h. The synthesized materials were labeled as CoMoO_(4) (3.6 mg), Ni-CoMoO_(4)-120 (3.93 mg), Ni-CoMoO_(4)-150 (3.46 mg),Ni-CoMoO_(4)-180 (4.88 mg), and Ni-CoMoO_(4)-200 (7.54 mg), respectively.Results and Discussion The XRD pattern of CoMoO_(4) shows that the diffraction peaks at 13.1°, 23.3°, 26.4°, 27.3°, 33.7°, 36.6°,38.9°, 41.7°, 47.4°, and 54.5° correspond to the crystal planes (001), (021), (002), (112) , (222) , (400), (040), (422), (222), (421),and (440) , respectively, of CoMoO_(4) (JCPDS 21–0868), indicating the effective synthesis of CoMoO_(4). However, CoMoO_(4) electrodematerial synthesized by in-situ Ni doping shows an overall shift of the XRD diffraction peak to the left. The SEM images show thatcompared to the undoped CoMoO_(4), Ni-doped CoMoO_(4) nanosheets at different reaction temperatures are uniformly nucleated andgrown on the surface of Ni foam due to Ni ions provided by the nickel foam as a crystallization core, and there is almost no porespace between the nanosheets. The nanosheets are stacked together with mutual reliance and supported. The results of specific surfacearea measurements indicate that in-situ Ni-doped CoMoO_(4) has the maximum specific surface area at a hydrothermal temperature of180 ℃. The results of CV and GCD tests show that the optimum specific capacitance of Ni-doped CoMoO_(4) electrode material can beobtained at 180 ℃.Conclusions In-situ Ni-doped CoMoO_(4) electrode materials were synthesized on acidified pretreated nickel foam by a hydrothermalmethod. The morphology of Ni-doped CoMoO_(4) electrode materials was controlled via modulating the hydrothermal temperatures (i.e.,120, 150, 180 ℃, and 200 ℃), in turn modulating the capacitive properties of CoMoO_(4) electrode materials. Compared to undopedCoMoO_(4), Ni-doped CoMoO_(4) nanosheets with different reaction temperatures uniformly nucleated and grew on the surface of nickelfoam due to Ni ions provided by nickel foam as a crystallization core, and the pores between nanosheets became smaller. Thenanosheets rely on each other to stack together and support. Ni-CoMoO_(4) was less prone to some problems like structural collapse andvolume deformation when subjected to long-cycle charging and discharging, showing a better cycling performance. The optimumcapacitance performance of Ni-doped CoMoO_(4) could be obtained at 180 ℃, with a high specific capacitance of 4680 mF·cm^(–2) at5 mA·cm^(–2). The capacitance retention of the ASC device after 10 000 cycles was 96%.
作者
李明伟
张洪旭
邹昱涵
LI Mingwei;ZHANG Hongxu;ZOU Yuhan(College of Materials Science and Engineering,Liaoning Technical University,Fuxin 123000,Liaoning,China)
出处
《硅酸盐学报》
北大核心
2025年第7期2013-2022,共10页
Journal of The Chinese Ceramic Society
基金
辽宁省科技厅应用基础研究项目(2023JH2/101300213)。
关键词
泡沫镍酸化预处理
原位镍掺杂
钼酸钴形貌控制
超级电容器
foam nickel acidification pretreatment
in-situ nickel doping
morphology control of cobalt molybdate
supercapacitor
