Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Roles of Fluorine-doping in Enhancing Initial Cycle Efficiency and SEI Formation of Li-, Al-cosubstituted Spinel Battery Cathodes

  • Nguyen, Cao Cuong (Department of Fine Chemical Engineering & Applied Chemistry, Chungnam National University) ;
  • Bae, Young-San (Department of Fine Chemical Engineering & Applied Chemistry, Chungnam National University) ;
  • Lee, Kyung-Ho (Department of Fine Chemical Engineering & Applied Chemistry, Chungnam National University) ;
  • Song, Jin-Woo (Graduate School of Green Energy Technology, Chungnam National University) ;
  • Min, Jeong-Hye (Graduate School of Green Energy Technology, Chungnam National University) ;
  • Kim, Jong-Seon (Department of Fine Chemical Engineering & Applied Chemistry, Chungnam National University) ;
  • Ko, Hyun-Seok (POSCO ES Materials) ;
  • Paik, Younkee (Korean Basic Science Institute) ;
  • Song, Seung-Wan (Department of Fine Chemical Engineering & Applied Chemistry, Chungnam National University)
  • Received : 2012.08.27
  • Accepted : 2012.11.07
  • Published : 2013.02.20
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Abstract

Fluorine-doping on the $Li_{1+x}Mn_{1.9-x}Al_{0.1}O_4$ spinel cathode materials is found to alter crystal shape, and enhance initial interfacial reactivity and solid electrolyte interphase (SEI) formation, leading to improved initial coulombic efficiency in the voltage region of 3.3-4.3 V vs. Li/$Li^+$ in the room temperature electrolyte of 1 M $LiPF_6$/EC:EMC. SEM imaging reveals that the facetting on higher surface energy plane of (101) is additionally developed at the edges of an octahedron that is predominantly grown with the most thermodynamically stable (111) plane, which enhances interfacial reactivity. Fluorine-doping also increases the amount of interfacially reactive $Mn^{3+}$ on both bulk and surface for charge neutrality. Enhanced interfacial reactivity by fluorine-doping attributes instant formation of a stable SEI layer and improved initial cyclic efficiency. The data contribute to a basic understanding of the impacts of composition on material properties and cycling behavior of spinel-based cathode materials for lithium-ion batteries.

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