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用于增强锂存储的富锂层状氧化物阴极的新型金属有机框架壳层衍生表面改性

Novel MOF shell-derived surface modification of Li-rich layered oxide cathode for enhanced lithium storage.

作者信息

Xiao Zhitong, Meng Jiashen, Li Qi, Wang Xuanpeng, Huang Meng, Liu Ziang, Han Chunhua, Mai Liqiang

机构信息

State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, International School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, China.

State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, International School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, China.

出版信息

Sci Bull (Beijing). 2018 Jan 15;63(1):46-53. doi: 10.1016/j.scib.2017.12.011. Epub 2017 Dec 13.

Abstract

Li-rich layered oxide materials have attracted increasing attention because of their high specific capacity (>250 mAh g). However, these materials typically suffer from poor cycling stability and low rate performance. Herein, we propose a facile and novel metal-organic-framework (MOF) shell-derived surface modification strategy to construct NiCo nanodots decorated (∼5 nm in diameter) carbon-confined LiMnNiCoO nanoparticles (LLO@C&NiCo). The MOF shell is firstly formed on the surface of as-prepared LiMnNiCoO nanoparticles via low-pressure vapor superassembly and then is in situ converted to the NiCo nanodots decorated carbon shell after subsequent controlled pyrolysis. The obtained LLO@C&NiCo cathode exhibits enhanced cycling and rate capability with a capacity retention of 95% after 100 cycles at 0.4 C and a high capacity of 159 mAh g at 5 C, respectively, compared with those of LLO (75% and 105 mAh g). The electrochemical impedance spectroscopy and selected area electron diffraction analyses after cycling demonstrate that the thin C&NiCo shell can endow LLO with high electronic conductivity and structural stability, indicating the undesired formation of the spinel phase initiated from the particle surface is efficiently suppressed. Therefore, this presented strategy may open a new avenue on the design of high-performance electrode materials for energy storage.

摘要

富锂层状氧化物材料因其高比容量(>250 mAh g)而受到越来越多的关注。然而,这些材料通常存在循环稳定性差和倍率性能低的问题。在此,我们提出了一种简便新颖的金属有机框架(MOF)壳层衍生表面改性策略,以构建由NiCo纳米点修饰(直径约5 nm)的碳包覆LiMnNiCoO纳米颗粒(LLO@C&NiCo)。首先通过低压气相超组装在制备好的LiMnNiCoO纳米颗粒表面形成MOF壳层,然后在后续的可控热解后原位转化为NiCo纳米点修饰的碳壳层。与LLO相比(75%和105 mAh g),所制备的LLO@C&NiCo正极分别在0.4 C下100次循环后容量保持率为95%,在5 C下具有159 mAh g的高容量,展现出增强的循环性能和倍率性能。循环后的电化学阻抗谱和选区电子衍射分析表明,薄的C&NiCo壳层能够赋予LLO高电子导电性和结构稳定性,这表明从颗粒表面引发的不期望的尖晶石相的形成得到了有效抑制。因此,所提出的策略可能为储能高性能电极材料的设计开辟一条新途径。

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