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계면안정화를 통한 Si-SiO<sub>2</sub>-흑연 복합재 음극의 전기화학적 특성 개선
민정혜,배영산,김성수,송승완,Min, Jeong-Hye,Bae, Young-San,Kim, Sung-Su,Song, Seung-Wan 한국전기화학회 2012 한국전기화학회지 Vol.15 No.3
Si계 음극소재는 리튬 삽입-탈착 중 일어나는 큰 구조적 부피변화와 입도변화로 인해 빠른 성능 퇴화가 일어나는 단점이 있다. 산화물 SiO 음극소재는 리튬과의 반응 중 비활성상인 $Li_2O$ 및 lithium silicate가 형성되어 Si의 부피변화를 완화시키는 버퍼 역할을 하므로 용량은 Si보다 적으나 개선된 용량 유지 특성을 보이는 것으로 알려져 있다. 본 연구에서는 Si의 부피변화 완화를 위하여 저가의 $SiO_2$와 입자간 전기전도성을 향상시키는 흑연을 구조안정화 기재로서 사용하여 Si-$SiO_2$-흑연 복합재 음극을 제작하였다. 구조안정화 뿐만 아니라 silane계 전해액 첨가제를 이용하여 Si-$SiO_2$-흑연 복합재 음극과 전해액간 계면을 안정화시킴으로써 용량 유지 특성이 개선되는 효과에 대해 보고하고자 한다. Structural volume change occurring on the Si-based anode battery materials during alloying/dealloying with lithium is noticed to be a major drawback responsible for a limited cycle life. Silicon monoxide has been reported to show relatively improved cycling performance compared to Si-containing materials for rechargeable lithium batteries, due to the structural buffering role of in-situ formed $Li_2O$ and lithium silicate during the reaction of silicon monoxide and lithium. Here we report improved cycling ability of interfacially stabilized Si-$SiO_2$-graphite composite anode using silane-based electrolyte additive for rechargeable lithium batteries, which includes low cost silicon dioxide for structural stabilization and graphite for enhanced conductivity.
Cao Cuong Nguyen,배영산,이경호,Jin-Woo Song,민정혜,김종선,Hyun-Seok Ko,백윤기,송승완 대한화학회 2013 Bulletin of the Korean Chemical Society Vol.34 No.2
Fluorine-doping on the Li1+xMn1.9-xAl0.1O4 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 LiPF6/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 Mn3+ 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 spinelbased cathode materials for lithium-ion batteries.