酸度控制的不同MnO_2的水热制备及电化学性能
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摘要
以KMnO_4为锰源、CO(NH2)2为还原剂,通过水热反应制备MnO_2,考察了体系酸度对产物结构和形貌的影响,应用X-射线衍射、扫描电镜和N2吸-脱附技术对产物进行表征。结果表明,在0～1 mol/L H2SO4溶液中,制备了颗粒状、球形、纤维状和海胆状MnO_2,前两种MnO_2为层状结构,后两种MnO_2具有隧道结构。海胆状MnO_2的比表面积高达95 m2/g。电化学测试结果显示,在0. 1 A/g的电流密度下,海胆状MnO_2首次放电比容量达到1318. 8 m Ah/g。恒流充放电140次后,容量保持率为74%。
MnO_2 were prepared by hydrothermal method using KMnO_4 as a manganese source and CO( NH2)2 as a reducing reagent. The effects of acidity on structure and morphology of products were investigated. The obtained products were characterized by X-ray diffraction,scanning electron microscopy and N2 adsorption-desorption. Results show that MnO_2 with different morphologies of particles,spheres,fibres and urchins were successfully prepared in 0-1 mol/L H_2SO_4 solution. The former two kinds of MnO_2 are layered structure,while the latter two kinds of MnO_2 are tunnel structure. And MnO_2 urchins have high specific surface area( 95 m2/g). Electrochemical measurements indicate MnO_2 urchins exhibit an initial discharge capacity of 1318. 8 m Ah/g at the current density of 0. 1 A/g. And the capacity retention reaches 74% after 140 cycles.
MnO_2 were prepared by hydrothermal method using KMnO_4 as a manganese source and CO( NH2)2 as a reducing reagent. The effects of acidity on structure and morphology of products were investigated. The obtained products were characterized by X-ray diffraction,scanning electron microscopy and N2 adsorption-desorption. Results show that MnO_2 with different morphologies of particles,spheres,fibres and urchins were successfully prepared in 0-1 mol/L H_2SO_4 solution. The former two kinds of MnO_2 are layered structure,while the latter two kinds of MnO_2 are tunnel structure. And MnO_2 urchins have high specific surface area( 95 m2/g). Electrochemical measurements indicate MnO_2 urchins exhibit an initial discharge capacity of 1318. 8 m Ah/g at the current density of 0. 1 A/g. And the capacity retention reaches 74% after 140 cycles.
引文
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[3] Yu P,Zhang X,Wang D,et al. Shape-Controlled Synthesis of 3D Hierarchical Mn O2Nanostructures for Electrochemical Supercapacitors[J].Crystal Growth&Design,2009,9(1):528-533.
[4] Zhang X,Yang W,Yang J,et al. Synthesis and Characterization ofα-Mn O2Nanowires:Self-Assembly and Phase Transformation toβ-Mn O2Microcrystals[J]. Journal of Crystal Growth,2008,310(3):716-722.
[5] Zhang Z,Zhao X,Li J. Facile Synthesis of Nanostructured MnO2as Anode Materials for Sodium-Ion Batteries[J]. Chem. Nano. Mat,2016,2(3):196-200.
[6] Zhu G,Deng L,Wang J,et al. The Simple Preparation of Birnessite-Type Manganese Oxide with Flower-Like Microsphere Morphology and Its Remarkable Capacity Retention[J]. Materials Research Bulletin,2012,47(11):3533-3537.
[7]朱刚,段淑娥,赵彤,等.α-Mn O2和β-MnO2一维材料的可控制备及其电容性能[J].人工晶体学报,2018,47(8):1675-1679.
[8] Wang N,Gao Y,Gong J,et al. Synthesis of Manganese Oxide Hollow Urchins with a Reactive Template of Carbon Spheres[J]. European Journal of Inorganic Chemistry,2008,2008(24):3827-3832.
[9] He X,Yang M,Ni P,et al. Rapid Synthesis of Hollow Structured MnO2Microspheres and Their Capacitance[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2010,363(1-3):64-70.
[10] Tao Y,Kanoh H,Abrams L,et al. Mesopore-Modified Zeolites:Preparation,Characterization,and Applications[J]. Chemical Reviews,2006,106(3):896-910.
[11]徐如人,庞文琴,于吉红,等.分子筛与多孔材料化学[M].北京:高等教育出版社,2004:146-147.
[12] Sung D Y,Kim I,Kim T,et al. Room Temperature Synthesis Routes to the 2D Nanoplates and 1D Nanowires/Nanorods of Manganese Oxides with Highly Stable Pseudocapacitance Behaviors[J]. The Journal of Physical Chemistry C,2011,115(27):13171-13179.
[13] Xu M,Kong L,Zhou W,et al. Hydrothermal Synthesis and Pseudocapacitance Properties ofα-Mn O2Hollow Spheres and Hollow Urchins[J].The Journal of Physical Chemistry C,2007,111(51):19141-19147.
[14] Gu X,Chen L,Ju Z,et al. Controlled Growth of Porousα-Fe2O3Branches onβ-Mn O2Nanorods for Excellent Performance in Lithium-Ion Batteries[J]. Advanced Functional Materials,2013,23(32):4049-4056.
[15] Zhou G,Wang D W,Li F,et al. Graphene-Wrapped Fe3O4Anode Material with Improved Reversible Capacity and Cyclic Stability for Lithium Ion Batteries[J]. Chemistry of Materials,2010,22(18):5306-5313.
[16] Nithyadharseni P,Reddy M V,Fanny H,et al. Facile One Pot Synthesis and Li-Cycling Properties of Mn O2[J]. RSC Advances,2015,5(74):60552-60561.
[17] Zhang W,Zhang B,Jin H,et al. Waste Eggshell as Bio-Template to Synthesize High Capacityδ-MnO2Nanoplatelets Anode for Lithium Ion Battery[J]. Ceramics International,2018,44(16):20441-20448.
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