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Spinel/Layered Heterostructured Lithium-Rich Oxide Nanowires as Cathode Material for High-Energy Lithium-Ion Batteries Ruizhi Yu, Xiaohui Zhang, Tao Liu, Li Yang, Lei Liu, Yu Wang, Xianyou Wang, Hongbo Shu, and Xiukang Yang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b11942 • Publication Date (Web): 08 Nov 2017 Downloaded from http://pubs.acs.org on November 8, 2017
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ACS Applied Materials & Interfaces
Spinel/Layered Heterostructured Lithium-Rich Oxide Nanowires as Cathode Material for High-Energy Lithium-Ion Batteries Ruizhi Yu, Xiaohui Zhang, Tao Liu, Li Yang, Lei Liu, Yu Wang, Xianyou Wang,∗ Hongbo Shu, Xiukang Yang (National Local Joint Engineering Laboratory for Key Materials of New Energy Storage Battery, National Base for International Science & Technology Cooperation, Hunan Province Key Laboratory of Electrochemical Energy Storage & Conversion, School of Chemistry, Xiangtan University, Xiangtan 411105, Hunan, China) ABSTRACT: Lithium-rich oxide material has been considered as an attractive candidate of high energy cathode for lithium-ion batteries (LIBs). However, the practical applications are still hindered due to its low initial reversible capacity, severe voltage decaying and unsatisfactory rate capability. Among all, the voltage decaying is a serious barrier which results in a large decrease of energy density during long term cycling. In order to overcome these issues, herein an efficient strategy of fabricating lithium rich oxide nanowires with spinel/layered heterostructure is proposed. Structural characterizations verify that the spinel/layered heterostructured nanowires are self-assembly of a lot of nanoparticles, and the Li4Mn5O12 spinel phase is embedded inside the layered structure. When the material is used as cathode of LIBs, the spinel/layered heterostructured nanowires can display an extremely high invertible capacity of 290.1 mA h g-1 at 0.1 C and suppressive voltage fading. Moreover, it exhibits a favorable cycling stability with capacity retention of 94.4 % after charging/discharging at 0.5 C for 200 cycles, and it shows extraordinary rate capability (183.9 mA h g-1, 10 C). The remarkable electrochemical properties can be connected with the spinel/layered heterostructure, which is in favor of Li+ transport kinetics and enhancing structural stability during cyclic process. KEYWORDS: lithium ion batteries, lithium-rich oxide nanowires, spinel/layered heterostructure, mitigated voltage fading, high rate capability
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Corresponding author: Xianyou Wang, Tel: +86 731 58293377; Fax: +86 731 58292052.
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1. INTRODUCTION Lithium-rich layered oxides (LLOs) have been extensively investigated over the last decades since these materials were first reported as cathodes of the Lithium ion batteries (LIBs) by Thackeray and Dahn.1-8 LLOs seem to be the most commercially valued candidate for next generation high energy density LIBs on account of their considerable reversible capacity of 250-300 mA h g-1 and extremely high working voltage of high than 4.5 V. The extremely high reversible capacity mainly derive from two mechanisms: one is the process of manganese redox (Mn3+/Mn4+), and the other is the reversible anionic redox reactions (O2-/O22- or O2-/O2n-, where 1
