흑연과 실리콘 일산화물의 혼합물로 구성된 리튬이온 이차전지용 음극의 사이클 성능개선 연구
Improvement of Cycle Performance of Graphite-Silicon Monoxide Mixture Negative Electrode in Lithium-ion Batteries
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초록
우수한 수명특성을 지니는 흑연과 높은 용량을 지니고 있는 실리콘 일산화물의 혼합전극을 제조하여 리튬이온 이차전지용 음극으로 적용하여 이의 사이클 성능에 대하여 평가하였다. 천연흑연과 실리콘 일산화물을 9:1의 질량비로 혼합하여 제조한 전극은 480 mAh g-1의 가역용량으로 천연흑연에 비하여 33% 이상의 높은 용량을 나타내었다. 그러나, 실리콘 일산화물의 부피변화로인하여 용량의 퇴화가 지속적으로 발생하였다. 본 연구에서는 전극 및 전해질의 구성에 변수들을적용하여 각각의 변수가 영향을 주는 전기화학적 특성을 파악하고 이를 통하여 사이클 수명을향상시킬 수 있는 방안을 모색하고자 하였다. 전극 제조 시에 poly(vinylidene fluoride) (PVdF) 바인더에 비하여 carboxymethyl cellulose (CMC) 바인더는 가장 우수한 사이클 특성을나타내었으며, CMC와 styrene-butadiene rubber (SBR)을 함께 사용하는 SBR/CMC 바인더의경우에는 CMC 단독 바인더를 사용하는 경우와 유사한 사이클 특성과 동시에 속도특성에서 장점을 지니고 있었다. 전해액 첨가제로 fluoroethylene carbonate (FEC)를 적용하는 경우에 수명특성이 크게 개선되었다. FEC의 함량이 10 질량%로 높아지게 되면 전지의 속도특성이 저하되기 때문에 5 질량%의 사용이 적절하였다. 또한 전극의 로딩값을 낮추게 되면 사이클 특성을 크게 향상시킬 수 있었으며, 집전체를 사포로 연마하여 거칠기를 증가시키는 것도 사이클 특성의개선을 가져올 수 있었다.
Abstract
Mixture electrodes of a graphite having a good cycle performance and a silicon monoxide (SiO) having a high capacity are fabricated and their cycle performances are evaluated as negative electrodes for lithium-ion batteries. The electrode prepared by mixing the natural graphite and carbon-coated SiO in a mass ratio of 9:1 shows a reversible capacity of 480 mAh g-1, 33% higher than that of graphite. However, the capacity deteriorates continuously upon cycling due to the volume change of silicon monoxide. In this study, the factors that can improve the cycle performance have been discussed through the change in the configurations of the electrode and the electrolyte. The electrode using the carboxymethyl cellulose (CMC) binder shows the best cycle performance compared to the conventional binders. The electrode sing the CMC and styrene-butadiene rubber (SBR) binder not only has almost the similar cycle characteristics with the electrode using the CMC binder but also has the better rate capability. When the fluoroethylene carbonate (FEC) is used as an electrolyte additive, the cycle life is improved. However, the electrolyte with 5 wt% of FEC is appropriate because the rate capability decreases when the content of FEC is increased to 10 wt%. In addition, when the mass loading of the electrode is lowered, the cycle performance is greatly improved. Also, enhanced cycle performance is achieved using the roughened Cu current collector polished by abrasive paper.
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