Nickel(Ni)-rich layered materials have attracted considerable interests as promising cathode materials for lithium ion batteries(LIBs)owing to their higher capacities and lower cost.Nevertheless,Mn-rich cathode materials usually suffer from poor cyclability caused by the unavoidable side-reactions between Ni^4+ions on the surface a nd electrolytes.The design of gradient concentration(GC)particles with Ni-rich inside and Mn-rich outside is proved to be an efficient way to address the issue.Herein,a series of LiNi0.6Co0.2Mn0.2O2(LNCM 622)materials with different GCs(the atomic ratio of Ni/Mn decreasing from the core to the outer layer)have been successfully synthesized via rationally designed co-precipitation process.Experimental results demonstrate that the GC of LNCM 622 materials plays an important role in their microstructure and electrochemical properties.The as-prepared GC3.5 cathode material with optimal GC can provide a shorter pathway for lithium-ion diffusion and stabilize the near-surface region,and finally achieve excellent electrochemical performances,delivering a discharge capacity over 176 mAh·g^-1 at 0.2 C rate and exhibiting capacity retention up to 94%after 100 cycles at 1 C.T h e rationally-designed co-precipitation process for fabricating the Ni-rich layered cathode materials with gradient composition lays a solid foundation for the preparation of high-performance cathode materials for LIBs.
For the ever-growing demand of advanced lithium-ion batteries, it is highly desirable to grow self-supported micro-/nanostructured arrays on metal substrates as electrodes directly. The in-situ growth of electrode materials on the conducting substrates greatly simplifies the electrode fabrication process without using any binders or conductive additives. Moreover, the well-ordered arrays closely connected to the current collectors can provide direct electron transport pathways and enhanced accommodation of strains arisen from lithium ion lithiation/delithiation. This article summarizes our recent work on design and construction of lithium-ion battery electrodes on metal substrates. An aqueous solution-based process and a microemulsion-mediated process have been respectively presented to control the kinetic and thermodynamic processes for the micro-/nanostructured array growth on metal substrates, with particular attention to CuO nanorod arrays and microcog arrays successfully prepared on Cu foil substrates. They can be directly used as binder-free electrodes to build advanced lithium-ion batteries with high energy, high safety and high stability.
Weixin ZhangYingmeng ZhangZeheng YangGongde ChenGuo MaQiang Wang
自制直径为90nm、长为500nm的β-FeOOH纳米棒为前驱物,通过碳热还原法和热分解法分别制备出形貌均匀、粒径为300nm的LiFePO4/C正极材料和粒径为100nm的Fe2O3负极材料,并研究它们对金属锂组成半电池和构造LiFePO4/C vs.Fe2O3全电池的电化学性能。结果表明:LiFePO4/C半电池在0.1C、0.5C、1.0C、5.0C、10.0C和15.0C(1C=170 mA g–1)倍率下放电比容量分别为158.8、153.2、144.3、126.8、111.0 mA h g–1和92.9mA h g–1。经过不同倍率循环后,返回0.1 C放电比容量为157.5mA h g–1,为初始0.1 C放电比容量的99.2%。Fe2O3半电池在50mA g–1电流密度下首次放电比容量为1655.5mA h g–1,循环50次后,仍保持460mA h g–1的放电比容量。LiFePO4/C vs.Fe2O3全电池在0.1 C倍率下,相对于LiFePO4活性物质,首次放电比容量为148.7mA h g–1;相对于Fe2O3活性物质,首次放电比容量为441.7mA h g–1。由LiFePO4/C纳米粒子作为正极材料、Fe2O3纳米粒子作为负极材料组成的全电池在0.1 C到2.0 C不同倍率下均表现出了良好的循环性能,且返回0.1 C后其放电比容量相对于初始0.1 C放电比容量无衰减。可见,以β-FeOOH纳米棒为前驱物控制制备的LiFePO4/C正极纳米材料和Fe2O3负极纳米材料可以有效地提升电池的性能。
