Li-Ni-Mn-O系锂离子电池正极材料纳米化及其电化学性能研究
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摘要
锂离子电池在电子系统、军事、航天和电动汽车等领域有着广泛的应用。正极材料的研制是锂离子电池技术的关键技术之一。虽然LiCoO_2由于容量高，可逆性和倍率性好成为商业化锂离子电池的主要正极材料，但其成本高，Co有毒，人们努力寻找一种可替换材料。
材料的纳米化呈现了多种新型物理特性。纳米电极材料在晶体结构、颗粒形貌及电化学性能等方面均表现出特殊的行为，也引起了各国学者的广泛关注。基于对锂离子电池正极材料纳米化可能出现的物理现象的认识和剖析为目的，本文以LiNi_(0．5)Mn_(0．5)O_2为体系对象，采用柠檬酸辅助溶胶-凝胶法制备纳米锂离子电池正极材料，优化最佳制备工艺，并采用多种测试表征手段对其结构性能进行研究，深入探讨电极材料纳米化对电化学性能的影响。
因此，本论文开展的研究内容包括：纳米结构形成方法与工艺、组成变化对结构和性能的影响。尝试通过将正极材料纳米化以后，在保持其具有较高容量及循环性能的基础上，通过细化晶粒，进而缩短锂离子在其内部的扩散路径，增大比表面积降低大电流下有效电流密度，从而提高材料的大电流倍率性能。实验在考察了不同的Li的掺入量，煅烧温度，保温时间等合成条件后，结果表明：初始原料中Li／(Mn+Ni)摩尔比为1．05，在900℃下煅烧10h所制得样品结构与电化学性能最佳。产物颗粒均匀，粒径在80nm左右。在2．5～4．5V之间，20mA／g的电流放电，体现出极佳的容量及循环保持率。与微米级材料相比，所合成纳米LiNi_(0．5)Mn_(0．5)O_2电极材料的大电流倍率性能有较大的改善。
采用电势阶跃法测量所合成纳米LiNi_(0．5)Mn_(0.5)O_2电极中的表观锂离子扩散系数，从理论上验证了纳米化后晶粒尺寸减小对增大锂离子扩散系数的促进作用。由于实验中测得的具有最大表观扩散系数的材料并非粒子尺寸最小的材料，于是本文在校正了尺度这一单纯几何因素对扩散系数的影响后，进一步探讨了纳米化后晶粒减小对材料本征扩散系数的影响。分析表明，材料的表观扩散能力同时受材料粒子的尺寸因素以及本征扩散能力因素两者共同影响，其变化规律是它们加合的结果。因此，在纳米材料的制备过程中不能片面的强调小尺度，在降低尺度的同时还需兼顾小尺寸对材料的离子扩散和容量性能的影响，只有在尺度和性能两者之间找到平衡点才可能真正的提升电极的实际性能。
Lithium-ion batteries are widely applied in electronic system, space technique, electric vehicle and military field. The positive electrode material is one of the most important technologies for lithium-ion battery. LiCoO_2 is being used as the cathode material in the majority of commercial lithium-ion batteries with good capacity, reversibility and rate capability, but it suffers from relatively high cost and the toxicity of cobalt. Lots of efforts have been made to develop possible alternatives as cathode.
Nanomaterials exhibit various new kinds of physical properties. Nanostructured electrodes have showed special properties in interior structure, morphology and electrochemical performance, which attract much attention by researchers all over the world. Based on purposes of realizing and analyzing the possible physical phenomena about nanostructured cathode of lithium-ion batteries, this thesis focus on LiNi_(0.5)Mn_(0.5)O_2 system and adopt citric acid assisted sol-gel method for synthesizing. The best synthesis techniques are optimized, the structure and properties of obtained sample is systematic studied by several characterization instruments. And the influence of nanostructured electrode toward the electrochemical performance is deeply explored.
Hence, this thesis involves the contents as follows: Formation method and technique about nanostructured materials; Influence of components variety toward structure and property. We attempt to synthesize nanostructured cathode which have fine capacity and cycle performance initially, then improve its high rate performance through both shorten diffusion path of Li~+ in grains and enhance specific surface area to decrease effective current density. The experiment contrast synthesis factors such as initial addition amount of Li, sintering temperature and time. The experiment results show that the sample of LiNi_(0.5)Mn_(0.5)O_2 which was sintered for 10h at 900℃from Li/(Ni+Mn)=1.05 in start material exhibits the best interior structure and electrochemical performance. The particles are uniform with size of about 80 nm and exhibit fine capacity and cycling retention in the voltage range of 2.5-4.5V at a specific current of 20mA/g. Comparing with micro-sized cathode material, this nanostructured LiNi_(0.5)Mn_(0.5)O_2 has improved performance at high rate charge-discharge.
The apparent diffusion coefficient of Li~+ in synthesized nanostructured LiNi_(0.5)Mn_(0.5)O_2 cathode was measured by potential step method. The promoting effect of decreased size of nano-crystallite toward the improvement of Li~+ diffusion coefficient is theoretically confirmed. Because the sample which has the highest apparent diffusion coefficient is not the minimum-sized one, this thesis correct the influence from size, which is geometrical factor, toward the apparent diffusion coefficient, then further discuss how decreased crystallite size influence intrinsic diffusion coefficient. Analysis shows that the apparent diffusion of materials is determined by both crystallite size factor and intrinsic diffusion factor. Its change law is the addition of those two factors. As a result, it is not optimum to unilaterally emphasize small crystallite size. The influence from small size toward ion diffusion and capacity of materials should also be considered during the synthesizing process. The improved practical performance of electrode would balance both crystallite size and property.
材料的纳米化呈现了多种新型物理特性。纳米电极材料在晶体结构、颗粒形貌及电化学性能等方面均表现出特殊的行为，也引起了各国学者的广泛关注。基于对锂离子电池正极材料纳米化可能出现的物理现象的认识和剖析为目的，本文以LiNi_(0．5)Mn_(0．5)O_2为体系对象，采用柠檬酸辅助溶胶-凝胶法制备纳米锂离子电池正极材料，优化最佳制备工艺，并采用多种测试表征手段对其结构性能进行研究，深入探讨电极材料纳米化对电化学性能的影响。
因此，本论文开展的研究内容包括：纳米结构形成方法与工艺、组成变化对结构和性能的影响。尝试通过将正极材料纳米化以后，在保持其具有较高容量及循环性能的基础上，通过细化晶粒，进而缩短锂离子在其内部的扩散路径，增大比表面积降低大电流下有效电流密度，从而提高材料的大电流倍率性能。实验在考察了不同的Li的掺入量，煅烧温度，保温时间等合成条件后，结果表明：初始原料中Li／(Mn+Ni)摩尔比为1．05，在900℃下煅烧10h所制得样品结构与电化学性能最佳。产物颗粒均匀，粒径在80nm左右。在2．5～4．5V之间，20mA／g的电流放电，体现出极佳的容量及循环保持率。与微米级材料相比，所合成纳米LiNi_(0．5)Mn_(0．5)O_2电极材料的大电流倍率性能有较大的改善。
采用电势阶跃法测量所合成纳米LiNi_(0．5)Mn_(0.5)O_2电极中的表观锂离子扩散系数，从理论上验证了纳米化后晶粒尺寸减小对增大锂离子扩散系数的促进作用。由于实验中测得的具有最大表观扩散系数的材料并非粒子尺寸最小的材料，于是本文在校正了尺度这一单纯几何因素对扩散系数的影响后，进一步探讨了纳米化后晶粒减小对材料本征扩散系数的影响。分析表明，材料的表观扩散能力同时受材料粒子的尺寸因素以及本征扩散能力因素两者共同影响，其变化规律是它们加合的结果。因此，在纳米材料的制备过程中不能片面的强调小尺度，在降低尺度的同时还需兼顾小尺寸对材料的离子扩散和容量性能的影响，只有在尺度和性能两者之间找到平衡点才可能真正的提升电极的实际性能。
Lithium-ion batteries are widely applied in electronic system, space technique, electric vehicle and military field. The positive electrode material is one of the most important technologies for lithium-ion battery. LiCoO_2 is being used as the cathode material in the majority of commercial lithium-ion batteries with good capacity, reversibility and rate capability, but it suffers from relatively high cost and the toxicity of cobalt. Lots of efforts have been made to develop possible alternatives as cathode.
Nanomaterials exhibit various new kinds of physical properties. Nanostructured electrodes have showed special properties in interior structure, morphology and electrochemical performance, which attract much attention by researchers all over the world. Based on purposes of realizing and analyzing the possible physical phenomena about nanostructured cathode of lithium-ion batteries, this thesis focus on LiNi_(0.5)Mn_(0.5)O_2 system and adopt citric acid assisted sol-gel method for synthesizing. The best synthesis techniques are optimized, the structure and properties of obtained sample is systematic studied by several characterization instruments. And the influence of nanostructured electrode toward the electrochemical performance is deeply explored.
Hence, this thesis involves the contents as follows: Formation method and technique about nanostructured materials; Influence of components variety toward structure and property. We attempt to synthesize nanostructured cathode which have fine capacity and cycle performance initially, then improve its high rate performance through both shorten diffusion path of Li~+ in grains and enhance specific surface area to decrease effective current density. The experiment contrast synthesis factors such as initial addition amount of Li, sintering temperature and time. The experiment results show that the sample of LiNi_(0.5)Mn_(0.5)O_2 which was sintered for 10h at 900℃from Li/(Ni+Mn)=1.05 in start material exhibits the best interior structure and electrochemical performance. The particles are uniform with size of about 80 nm and exhibit fine capacity and cycling retention in the voltage range of 2.5-4.5V at a specific current of 20mA/g. Comparing with micro-sized cathode material, this nanostructured LiNi_(0.5)Mn_(0.5)O_2 has improved performance at high rate charge-discharge.
The apparent diffusion coefficient of Li~+ in synthesized nanostructured LiNi_(0.5)Mn_(0.5)O_2 cathode was measured by potential step method. The promoting effect of decreased size of nano-crystallite toward the improvement of Li~+ diffusion coefficient is theoretically confirmed. Because the sample which has the highest apparent diffusion coefficient is not the minimum-sized one, this thesis correct the influence from size, which is geometrical factor, toward the apparent diffusion coefficient, then further discuss how decreased crystallite size influence intrinsic diffusion coefficient. Analysis shows that the apparent diffusion of materials is determined by both crystallite size factor and intrinsic diffusion factor. Its change law is the addition of those two factors. As a result, it is not optimum to unilaterally emphasize small crystallite size. The influence from small size toward ion diffusion and capacity of materials should also be considered during the synthesizing process. The improved practical performance of electrode would balance both crystallite size and property.
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