D0L:10.13374h.issn1001-053x.2013.10.020 第35卷第10期 北京科技大学学报 Vol.35 No.10 2013年10月 Journal of University of Science and Technology Beijing 0ct.2013 二氧化锰微纳米球和微米棒的制备工艺优化及性能 张勇1,2)心，李光胤，高海丽)，张建)，黄淑荣4)，王力臻12)，宋延华1) 1)郑州轻工业学院材料与化学工程学院，郑州4500022)河南省表界面科学重点实验室，郑州450002 3)中航飞机股份有限公司汉中飞机分公司机械动力公司，汉中723215 4)中航飞机股份有限公司汉中飞机分公司精修站，汉中723215 ☒通信作者，E-mail:zy@zzui.edu.cn 摘要采用一种简便、快速和低温的水热法制备了超级电容器用MO2微纳米球和微米棒粉体颗粒，并用正交试验和 单因素实验对其制备工艺进行了优化。通过X射线衍射、扫描电镜和电化学测试，研究了所得材料的晶体结构、表面形 貌和超电容性能.最佳合成工艺条件为：反应温度150℃，KMnO4/小MnCl2摩尔比2.5：1.0，反应时间3h,填充率40%。 该工艺下所制的样品为a-MnO2,且呈现出空心、表面多孔的微纳米球和微米棒形貌.微纳米球的直径约为020.8um, 微米棒的直径约为30nm、长约为5um.在此条件下，所得样品在100、150、200、250和300mAg1电流密度下，第 5次的放电比电容分别为255、170、133、105和88Fg-1,其等效串联电阻和电荷转移电阻分别为0.37和0.402. 关键词二氧化锰：微米球：纳米球：微米棒：水热合成：超级电容器 分类号TM533 Preparation process optimization and properties of manganese dioxide micro/nano spheres and microrods ZHANG Yong2),LI Guang-yin),GAO Hai-i),ZHANG Jian,HUANG Shu-rong),WANG Li-zhen), SONG Yan-hual) 1)Department of Material and Chemical Engineering,Zhengzhou University of Light Industry,Zhengzhou 450002,China 2)Henan Provincial Key Laboratory of Surface Interface Science,Zhengzhou 450002,China 3)Mechanical Power Company,AVIC Aircraft Corporation Hanzhong Aircraft Company,Hanzhong 723215,China 4)Refined Station,AVIC Aircraft Corporation Hanzhong Aircraft Company,Hanzhong 723215,China Corresponding author,E-mail:zy@zzuli.edu.cn ABSTRACT MnO2 powders with micro/nano spheres and microrods for supercapacitors were synthesized via a simple,quick and low-temperature hydrothermal method.Their preparation process was optimized by orthorhombic test and single factor experiment.The crystalline structure,surface morphology and supercapacitive properties of the as-prepared MnO2 powders were studied by X-ray diffraction,scanning electron microscopy and electrochemical measurement.Experimental results show that the optimal reaction conditions are the reaction temperature of 150 C, the KMnO/MnCl molar ratio of 2.5:1.0,the reaction time of 3 h,and the filling factor of 40%.Under the optimal conditions,the as-prepared MnO2 powders have typical a-MnO2 structure with hollow and porous micro/nano spheres and microrods.The o-MnO2 micro/nano sphere diameter is about from 0.2 to 0.8 um,while the a-MnO2 microrods have the diameter of 30 nm and the length of 5 um.The discharge specific capacitance of products at the 5th discharge cycle retains 255,170,133,105 and 88 Fg at current densities of 100,150,200,250 and 300 mA.g,respectively.Moreover, the values of equivalent series resistance and charge transfer resistance decrease to 0.37 n and 0.40 n,respectively. KEY WORDS manganese dioxide;microspheres;nanospheres;microrods;hydrothermal synthesis;supercapacitors 收稿日期：2012-09-16 基金项目：国家自然科学基金资助项目(21001097)：河南省高校科技创新人才支持计划资助项目(2012 HASTIT022):河南省科技 厅基础与前沿技术研究项目(102300410107)：河南省高等学校青年骨干教师资助计划项目（豫教高[2009844号）第 35 卷 第 10 期 北 京 科 技 大 学 学 报 Vol. 35 No. 10 2013 年 10 月 Journal of University of Science and Technology Beijing Oct. 2013 二氧化锰微纳米球和微米棒的制备工艺优化及性能 张 勇1,2) ，李光胤1)，高海丽1)，张 建3)，黄淑荣4)，王力臻1,2)，宋延华1) 1) 郑州轻工业学院材料与化学工程学院，郑州 450002 2) 河南省表界面科学重点实验室，郑州 450002 3) 中航飞机股份有限公司汉中飞机分公司机械动力公司，汉中 723215 4) 中航飞机股份有限公司汉中飞机分公司精修站，汉中 723215 通信作者，E-mail: zy@zzuli.edu.cn 摘 要 采用一种简便、快速和低温的水热法制备了超级电容器用 MnO2 微纳米球和微米棒粉体颗粒，并用正交试验和 单因素实验对其制备工艺进行了优化。通过 X 射线衍射、扫描电镜和电化学测试，研究了所得材料的晶体结构、表面形 貌和超电容性能. 最佳合成工艺条件为：反应温度 150 ℃，KMnO4/MnCl2 摩尔比 2.5:1.0，反应时间 3 h，填充率 40%。 该工艺下所制的样品为 α-MnO2，且呈现出空心、表面多孔的微纳米球和微米棒形貌. 微纳米球的直径约为 0.2∼0.8 µm， 微米棒的直径约为 30 nm、长约为 5 µm. 在此条件下，所得样品在 100、150、200、250 和 300 mA·g −1 电流密度下，第 5 次的放电比电容分别为 255、170、133、105 和 88 F·g −1，其等效串联电阻和电荷转移电阻分别为 0.37 和 0.40 Ω. 关键词 二氧化锰；微米球；纳米球；微米棒；水热合成；超级电容器 分类号 TM533 Preparation process optimization and properties of manganese dioxide micro/nano spheres and microrods ZHANG Yong1,2) , LI Guang-yin1), GAO Hai-li1), ZHANG Jian3), HUANG Shu-rong4), WANG Li-zhen1,2) , SONG Yan-hua1) 1) Department of Material and Chemical Engineering, Zhengzhou University of Light Industry, Zhengzhou 450002, China 2) Henan Provincial Key Laboratory of Surface & Interface Science, Zhengzhou 450002, China 3) Mechanical Power Company, AVIC Aircraft Corporation Hanzhong Aircraft Company, Hanzhong 723215, China 4) Refined Station, AVIC Aircraft Corporation Hanzhong Aircraft Company, Hanzhong 723215, China Corresponding author, E-mail: zy@zzuli.edu.cn ABSTRACT MnO2 powders with micro/nano spheres and microrods for supercapacitors were synthesized via a simple, quick and low-temperature hydrothermal method. Their preparation process was optimized by orthorhombic test and single factor experiment. The crystalline structure, surface morphology and supercapacitive properties of the as-prepared MnO2 powders were studied by X-ray diffraction, scanning electron microscopy and electrochemical measurement. Experimental results show that the optimal reaction conditions are the reaction temperature of 150 ℃, the KMnO4/MnCl2 molar ratio of 2.5:1.0, the reaction time of 3 h, and the filling factor of 40%. Under the optimal conditions, the as-prepared MnO2 powders have typical α-MnO2 structure with hollow and porous micro/nano spheres and microrods. The α-MnO2 micro/nano sphere diameter is about from 0.2 to 0.8 µm, while the α-MnO2 microrods have the diameter of 30 nm and the length of 5 µm. The discharge specific capacitance of products at the 5th discharge cycle retains 255, 170, 133, 105 and 88 F·g −1 at current densities of 100, 150, 200, 250 and 300 mA·g −1 , respectively. Moreover, the values of equivalent series resistance and charge transfer resistance decrease to 0.37 Ω and 0.40 Ω, respectively. KEY WORDS manganese dioxide; microspheres; nanospheres; microrods; hydrothermal synthesis; supercapacitors 收稿日期：2012-09-16 基金项目：国家自然科学基金资助项目 (21001097)；河南省高校科技创新人才支持计划资助项目 (2012HASTIT022)；河南省科技 厅基础与前沿技术研究项目 (102300410107)；河南省高等学校青年骨干教师资助计划项目 (豫教高 [2009]844 号) DOI:10.13374/j.issn1001-053x.2013.10.020