층상계 산화물 양극의 4.6 V 고전압 특성 향상에서의 Sulfone 첨가제의 역할
Role of Sulfone Additive in Improving 4.6V High-Voltage Cycling Performance of Layered Oxide Battery Cathode
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층상구조 삼성분계 LiNi1-x-yCoxMnyO2 양극활물질을 4.3 V 이상 고전압으로 충전시키면 용량 증가를 기대할 수 있으나 기존 전해액의 산화안정성이 낮아 고전압 성능 구현에 제한이 있다. 본연구에서는 설폰계 전해액 첨가제인 dimethyl sulfone (DMS), diethyl sulfone (DES), ethyl methyl sulfone (EMS)을 사용하여 LiNi0.5Co0.2Mn0.3O2 양극의 고전압 특성을 향상시키고자 한다. 본 논문은 다양한 선형 sulfone계 첨가제가 포함된 전해액에서 3.0-4.6 V 전압범위에서 양극의 충방전 특성과 양극-전해액간 계면거동과 표면층 분석에 대한 내용으로 이루어져 있다. 특히Dimethyl sulfone (DMS) 첨가제 사용시, 50 사이클 중 198-173 mAhg-1의 방전 용량과 87% 의 용량유지율을 보여 기존 전해액 대비 상당히 향상된 충방전 안정성을 보였다. 표면조성 분광분석 결과, DMS 첨가제 사용시 양극에 안정한 표면보호층이 형성되고 금속 용출이 억제되어고전압 충방전 특성이 향상되었음 알 수 있었다.
Abstract
Capacity of layered lithium nickel-cobalt-manganese oxide (LiNi1-x-yCoxMnyO2) cathode material can increase by raising the charge cut-off voltage above 4.3 V vs. Li/Li+, but it is limited due to anodic instability of conventional electrolyte. We have been screening and evaluating various sulfone-based compounds of dimethyl sulfone (DMS), diethyl sulfone (DES), ethyl methyl sulfone (EMS) as electrolyte additives for high-voltage applications. Here we report improved cycling performance of LiNi0.5Co0.2Mn0.3O2 cathode by the use of dimethyl sulfone (DMS) additive under an aggressive charge condition of 4.6 V, compared to that in conventional electrolyte, and cathode-electrolyte interfacial reaction behavior. The cathode withDMS delivered discharge capacities of 198–173 mAhg–1 over 50 cycles and capacity retention of 84%. Surface analysis results indicate that DMS induces to form a surface protective film at the cathode and inhibit metal-dissolution, which is correlated to improved high–voltage cycling performance.
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