Core–Shell Structure and Interaction Mechanism of γ‐MnO2 Coated Sulfur for Improved Lithium‐Sulfur Batteries. Issue 14 (30th January 2017)

• Record Type: Journal Article
• Authors: Ni, Lubin; Wu, Zhen; Zhao, Gangjin; Sun, Chunyu; Zhou, Chuanqiang; Gong, XiangXiang; Diao, Guowang
• Is Part Of: Small. Volume 13:Issue 14(2017)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2017-01-30
• Subjects: core–shells -- γ‐MnO2 -- interaction mechanisms -- lithium‐sulfur batteries -- Mn3O4 -- phase transformation; Nanotechnology -- Periodicals; Nanoparticles -- Periodicals; Microtechnology -- Periodicals; 620.5
• DOI: 10.1002/smll.201603466
• Languages: English
• ISSNs: 1613-6810

Abstract

Abstract : Lithium‐sulfur batteries have attracted worldwide interest due to their high theoretical capacity of 1672 mAh g −1 and low cost. However, the practical applications are hampered by capacity decay, mainly attributed to the polysulfide shuttle. Here, the authors have fabricated a solid core–shell γ‐MnO2 ‐coated sulfur nanocomposite through the redox reaction between KMnO4 and MnSO4 . The multifunctional MnO2 shell facilitates electron and Li + transport as well as efficiently prevents polysulfide dissolution via physical confinement and chemical interaction. Moreover, the γ‐MnO2 crystallographic form also provides one‐dimensional (1D) tunnels for the Li + incorporation to alleviate insoluble Li2 S2 /Li2 S deposition at high discharge rate. More importantly, the MnO2 phase transformation to Mn3 O4 occurs during the redox reaction between polysulfides and γ‐MnO2 is first thoroughly investigated. The S@γ‐MnO2 composite exhibits a good capacity retention of 82% after 300 cycles (0.5 C) and a fade rate of 0.07% per cycle over 600 cycles (1 C). The degradation mechanism can probably be elucidated that the decomposition of the surface Mn3 O4 phase is the cause of polysulfide dissolution. The recent work thus sheds new light on the hitherto unknown surface interaction mechanism and the degradation mechanism of Li‐S cells. Abstract : The multifunctional γ‐MnO2 shell as an efficient sulfur host can prevent polysulfide shuttle via physical confinement and chemical interaction. Comprehensive analytical studies identify the new surface interaction mechanism of phase evolution from MnO2 to Mn3 O4 on the host surface and the following surface degradation mechanism in Li‐S cells. This sheds new light on the practical application of the low‐cost, high‐energy, and long‐life Li‐S batteries.