锰氧化物纳微米材料的合成与性能表征
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摘要
本论文研究了α-MnO_2纳米棒、α-MnO_2球和尖晶石LiMn_2O_4微球的合成，并对所得样品的电化学性能进行了表征。具体工作如下：
采用简单的水热法在酸性体系下分解KMnO_4制备了单晶的α-MnO_2纳米棒。SEM和TEM结果表明，所合成α-MnO_2纳米棒的直径约30～70 nm，最大长度约2．6μm。通过分析不同水热反应时间所得MnO_2产物的相结构和微观形貌，提出α-MnO_2纳米棒的形成应经历了一“团聚—溶解—重结晶—各向异性生长—奥斯特瓦尔德熟化”过程。同时详细考察了各种实验条件对产物晶型和形貌的影响。电化学性能研究发现水热反应5和8 h所合成MnO_2产物的电容行为较好，初始放电比容量分别为84.9和75.3 F╱g。模拟锌锰电池测试发现所合成的α-MnO_2纳米棒具有良好的放电性能，在62.5和375 mA／g速率下的放电比容量分别为278和235 mAh／g。
通过温和的湿化学法合成了α-MnO_2球。SEM和TEM分析表明所合成产物是由直径0.3～3μm的球形颗粒构成。条件实验发现温和的反应条件更有利于α-MnO_2球的形成，随着反应温度的升高，所得产物的形貌也将发生变化，讨论了α-MnO_2球的形成机理。模拟锂离子电池性能研究表明，在室温下所合成的α-MnO_2具有良好的电化学性能，其初始放电比容量为206.2 mAh／g，15次循环后的放电比容量仍为154.7 mAh／g。模拟锌锰电池测试发现70℃条件下所得α-MnO_2产物具有良好的放电特性，在50和500 mA／g速率下的放电比容量分别为280和168 mAh／g。
以所制备的α-MnO_2球为前驱体，分别采用溶剂热反应和高温固相反应合成了LiMn_2O_4产物。SEM分析发现溶剂热合成的LiMn_2O_4形貌较不规则，主要为多面体颗粒；而高温固相法合成的LiMn_2O_4材料保持了好的球形形貌，颗粒尺寸为1～10μm。模拟锂离子电池性能研究表明，高温固相反应合成的LiMn_2O_4微球的电化学性能优于溶剂热反应合成的LiMn_2O_4产物。
In this dissertation,α-MnO_2 nanorods,α-MnO_2 spheres, and spinel LiMn_2O_4 microspheres have been synthesized, respectively. Their electrochemical properties have been characterized, accordingly. The details are presented as follows.
Firstly, single-crystalα-MnO_2 nanorods were prepared by simple hydrothermal decomposition of KMnO_4 under acidic conditions. SEM and TEM images indicate that the as-synthesizedα-MnO_2 products are composed of nanorods with diameters 30-70 nm and have a length up to2.6μm. The growth process of the MnO_2 nanorods was studied by analyzing phase structures and morphologies of the products obtained at different reaction stages. An "agglomeration-dissolution/recrystallization-anisotropic growth-Ostwald ripening" process was proposed to explain the formation ofα-MnO_2 nanorods. Meantime, the effects of various experimental parameters on the phases and morphologies of the final products were investigated in detail. Electrochemical studies show that the MnO_2 nanorods prepared for 5 and 8 h exhibit ideal capacitive behaviors with initial discharge capacities of 84.9 and 75.3 F/g, respectively. In addition, the as-preparedα-MnO_2 nanorods display fine discharge characteristics in laboratory-made Zn-MnO_2 cells. The discharge capacities of theα-MnO_2 nanorods are 278 and 235 mAh/g, respectively, at current rates of 62.5 and 375 mA/g, accordingly.
Secondly,α-MnO_2 spheres were synthesized by a mild wet chemical method. SEM and TEM images indicate that the resultant products consist of spherical particles with diameters ranging from 0.3 to 3μm. It is found that the mild reaction condition favors the formation ofα-MnO_2 spheres and the morphologies of the MnO_2 products vary with the increase of reaction temperatures. The formation of theα-MnO_2 spheres was discussed based on the experimental results. Electrochemical studies show that theα-MnO_2 nanorods obtained at room temperature exhibit fine electrochemical properties in laboratory-made Li-ion cells. The initial discharge capacity was 206.2 mAh/g and the discharge capacity retained 154.7 mAh/g over 15 cycles. In addition, it is seen that the products prepared at 70℃show excellent discharge characteristics in laboratory-made Zn-MnO_2 cells with discharge capacities of 280 and 235 mAh/g, respectively, at current rates of 50 and 500 mA/g, accordingly.
Thirdly, spinel LiMn_2O_4 products were synthesized by solvothermal and high temperature solid-state reaction, respectively, by using the pre-obtainedα-MnO_2 spheres as precursors. SEM images indicate that the resulting products prepared by solvothermal reaction exhibit irregular shapes while the products obtained by solid-state reaction are microspheres having diameters of 1-10μm. Electrochemical studies show that the LiMn_2O_4 products prepared by solid-state reaction exhibit better electrochemical properties that that prepared by solvothermal method.
采用简单的水热法在酸性体系下分解KMnO_4制备了单晶的α-MnO_2纳米棒。SEM和TEM结果表明，所合成α-MnO_2纳米棒的直径约30～70 nm，最大长度约2．6μm。通过分析不同水热反应时间所得MnO_2产物的相结构和微观形貌，提出α-MnO_2纳米棒的形成应经历了一“团聚—溶解—重结晶—各向异性生长—奥斯特瓦尔德熟化”过程。同时详细考察了各种实验条件对产物晶型和形貌的影响。电化学性能研究发现水热反应5和8 h所合成MnO_2产物的电容行为较好，初始放电比容量分别为84.9和75.3 F╱g。模拟锌锰电池测试发现所合成的α-MnO_2纳米棒具有良好的放电性能，在62.5和375 mA／g速率下的放电比容量分别为278和235 mAh／g。
通过温和的湿化学法合成了α-MnO_2球。SEM和TEM分析表明所合成产物是由直径0.3～3μm的球形颗粒构成。条件实验发现温和的反应条件更有利于α-MnO_2球的形成，随着反应温度的升高，所得产物的形貌也将发生变化，讨论了α-MnO_2球的形成机理。模拟锂离子电池性能研究表明，在室温下所合成的α-MnO_2具有良好的电化学性能，其初始放电比容量为206.2 mAh／g，15次循环后的放电比容量仍为154.7 mAh／g。模拟锌锰电池测试发现70℃条件下所得α-MnO_2产物具有良好的放电特性，在50和500 mA／g速率下的放电比容量分别为280和168 mAh／g。
以所制备的α-MnO_2球为前驱体，分别采用溶剂热反应和高温固相反应合成了LiMn_2O_4产物。SEM分析发现溶剂热合成的LiMn_2O_4形貌较不规则，主要为多面体颗粒；而高温固相法合成的LiMn_2O_4材料保持了好的球形形貌，颗粒尺寸为1～10μm。模拟锂离子电池性能研究表明，高温固相反应合成的LiMn_2O_4微球的电化学性能优于溶剂热反应合成的LiMn_2O_4产物。
In this dissertation,α-MnO_2 nanorods,α-MnO_2 spheres, and spinel LiMn_2O_4 microspheres have been synthesized, respectively. Their electrochemical properties have been characterized, accordingly. The details are presented as follows.
Firstly, single-crystalα-MnO_2 nanorods were prepared by simple hydrothermal decomposition of KMnO_4 under acidic conditions. SEM and TEM images indicate that the as-synthesizedα-MnO_2 products are composed of nanorods with diameters 30-70 nm and have a length up to2.6μm. The growth process of the MnO_2 nanorods was studied by analyzing phase structures and morphologies of the products obtained at different reaction stages. An "agglomeration-dissolution/recrystallization-anisotropic growth-Ostwald ripening" process was proposed to explain the formation ofα-MnO_2 nanorods. Meantime, the effects of various experimental parameters on the phases and morphologies of the final products were investigated in detail. Electrochemical studies show that the MnO_2 nanorods prepared for 5 and 8 h exhibit ideal capacitive behaviors with initial discharge capacities of 84.9 and 75.3 F/g, respectively. In addition, the as-preparedα-MnO_2 nanorods display fine discharge characteristics in laboratory-made Zn-MnO_2 cells. The discharge capacities of theα-MnO_2 nanorods are 278 and 235 mAh/g, respectively, at current rates of 62.5 and 375 mA/g, accordingly.
Secondly,α-MnO_2 spheres were synthesized by a mild wet chemical method. SEM and TEM images indicate that the resultant products consist of spherical particles with diameters ranging from 0.3 to 3μm. It is found that the mild reaction condition favors the formation ofα-MnO_2 spheres and the morphologies of the MnO_2 products vary with the increase of reaction temperatures. The formation of theα-MnO_2 spheres was discussed based on the experimental results. Electrochemical studies show that theα-MnO_2 nanorods obtained at room temperature exhibit fine electrochemical properties in laboratory-made Li-ion cells. The initial discharge capacity was 206.2 mAh/g and the discharge capacity retained 154.7 mAh/g over 15 cycles. In addition, it is seen that the products prepared at 70℃show excellent discharge characteristics in laboratory-made Zn-MnO_2 cells with discharge capacities of 280 and 235 mAh/g, respectively, at current rates of 50 and 500 mA/g, accordingly.
Thirdly, spinel LiMn_2O_4 products were synthesized by solvothermal and high temperature solid-state reaction, respectively, by using the pre-obtainedα-MnO_2 spheres as precursors. SEM images indicate that the resulting products prepared by solvothermal reaction exhibit irregular shapes while the products obtained by solid-state reaction are microspheres having diameters of 1-10μm. Electrochemical studies show that the LiMn_2O_4 products prepared by solid-state reaction exhibit better electrochemical properties that that prepared by solvothermal method.
引文
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