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摘要:
利用水热法合成了Zn-Mn氧化物前驱体，在温度400、500、600、700℃下，空气气氛中煅烧前驱体，以此来制备纳米片组装成的分级多孔结构的ZnMn2O4微球。其中，在500℃空气中煅烧前驱体制备的ZnMn2O4（ZMO-500）微球具有丰富的多级次孔结构，其作为锂离子电池负极材料，在500 mA/g的电流密度下，ZMO-500微球负极材料循环500次以后仍具有1 132 mAh/g高的放电比容量。ZMO-500负极材料优异的电化学性能得益于其分级多孔结构，不仅可以增加电极和电解质之间的接触面积以促进锂离子的迁移，而且还为循环过程中电极体积膨胀提供足够的缓冲空间。
Abstract:The precursor of Zn-Mn oxides were synthesized by a facile hydrothermal method and subsequently calcined at different temperature of 400℃, 500℃, 600℃ and 700℃ in air in order to synthesis the hierarchical porous ZnMn2O4 microspheres assembled by a lot of nanosheets. The ZnMn2O4 microspheres synthesized by calcining precursor in air at 500℃ (ZMO-500) display rich hierarchical porous structures, and when used as the anode material of lithium ion batteries, ZMO-500 microsphere anode material exhibits a high discharge capacity of 1 132 mAh/g after 500 cycles at a current density of 500 mA/g. It is believed that the outstanding electrochemical performance of ZMO-500 microsphere anode material benefits from the hierarchical porous structure that can not only increase the contact area between the electrode and the electrolyte to facilitate the transfer of Li+, but also provide sufficient space for volume expansion of the electrode during the cyclic process.
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Key words:
- hydrothermal synthesis /
- ZnMn2O4 /
- hierarchical porous microsphere /
- anode /
- lithium ion batteries
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图 1 Zn-Mn氧化物前驱体在低倍和高倍下的SEM照片
Figure 1. Low-magnification and high-magnification SEM images of precursor of Zn-Mn oxides
图 2 Zn-Mn氧化物前驱体XRD图谱和DSC-TG曲线
Figure 2. XRD pattern and DSC-TG curves of precursor of Zn-Mn oxides
图 4 ZMO-500在低倍和高倍下的SEM照片, TEM和HRTEM照片，以及ZMO-500材料N2吸脱附曲线(插图为ZMO-500的孔径分布)
Figure 4. Low-magnification and high-magnification SEM images, TEM image and HRTEM image of ZMO-500, N2 adsorption/desorption isotherm of ZMO-500 (inset of ZMO-500 pore size distribution)
图 6 ZMO-500电极的CV曲线、放-充电曲线和循环性能
Figure 6. CV curves, discharge-charge curves and cycling performance of ZMO-500 electrode
图 7 ZMO-400, ZMO-500, ZMO-600和ZMO-700在500 mA/g电流密度下的循环性能比较
Figure 7. Comparison of cycle performance among ZMO-400, ZMO-500, ZMO-600 and ZMO-700 at 500 mA/g
图 8 不同循环次数下在中-高频ZMO-500电极的EIS数据(插图为放大图)，及阻抗曲线的实部值与低频区角频率的倒数平方根关系曲线
Figure 8. EIS data and its enlargement (inset) at medium-high frequency region for different cycles, plot of real part of impedance as a function of reciprocal root square of lower angular frequencies
图 9 ZMO-500电极在500 mA/g下循环500次以后低倍和高倍SEM照片
Figure 9. Low-magnification and high-magnification SEM images of ZMO-500 electrode after 500 cycles at 500 mA/g
表 1 不同循环次数ZMO-500电极的Warburg阻抗系数和锂离子扩散系数
Table 1. Warburg impedance coefficient and lithium ion diffusion coefficient of ZMO-500 electrodes at different cycles
循环次数 σ/(Ω·cm2·s-0.5) D/(cm2·s-1) 第1次 36.17 1.70×10-14 第50次 66.66 4.99×10-15 第200次 36.37 1.68×10-14 
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