전해액 첨가제가 흑연 음극의 저온특성에 미치는 영향
The Roles of Electrolyte Additives on Low-temperature Performances of Graphite Negative Electrode
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표준 전해액에 2중량%의 VC(vinylene carbonate)와 FEC(fluoroethylene carbonate)를 각각 첨가한전해액으로부터 흑연 음극 표면에 SEI(solid electrolyte interphase) 층을 형성시키고, SEI 특성에따른 흑연 음극의 저온(−30oC) 충방전 특성을 조사하였다. 흑연의 충·방전 용량은 FEC를 첨가한전해액, 표준 전해액, 그리고 VC를 첨가한 전해액의 순서로 감소하였고, 충·방시 발생하는 과전압은 반대경향을 보이며 증가하였다. 이는 첨가제의 종류에 따라 생성된 SEI 층의 저항과 전하전달저항에 차이가 있음을 설명하는데, 이를 SEI 층의 화학 조성과 두께를 비교하여 확인하였다. 표준전해액으로부터 생성된 SEI 층은 C-O 성분을 포함하는 고분자 형태의 화합물과 리튬 염의 환원분해로 생성된 LixPFyOz 등으로 구성되었다. VC를 포함한 전해액으로부터 생성된 SEI 층은 C-O 화합물 비율이 높고 조밀하여 리튬 염의 분해가 억제되어 얇은 피막이 생성됨에도 불구하고 가장 큰저항 값을 보였다. 반면에 FEC로부터 생성된 SEI 층은 C-O 성분의 비율이 VC를 첨가한 전해액의경우보다는 작으면서도 리튬 염의 분해가 크지 않아서, 리튬 이온의 이동이 가장 용이한 피막을 형성하고 있어 가장 낮은 피막저항 및 전하전달 저항을 나타내었다. 결론적으로 FEC를 첨가제로 사용한 경우 생성된 SEI 층의 저항이 가장 작아서 흑연 음극의 저온특성이 가장 우수하였다.
Abstract
SEI (solid electrolyte interphase) layers are generated on a graphite negative electrode from three different electrolytes and low-temperature (−30oC) charge/discharge performance of the graphite electrode is examined. The electrolytes are prepared by adding 2 wt% of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) into a standard electrolyte solution. The charge-discharge capacity of graphite electrode shows the following decreasing order; FEC-added one > standard > VC-added one. The polarization during a constant-current charging shows the reverse order. These observations illustrate that the SEI film resistance and charge transfer resistance differ according to the used additives. This feature has been confirmed by analyzing the chemical composition and thickness of three SEI layers. The SEI layer generated from the standard electrolyte is composed of polymeric carbon-oxygen species and the decomposition products (LixPFyOz) of lithium salt. The VC-derived surface film shows the largest resistance value even if the salt decomposition is not severe due to the presence of dense film comprising C-O species. The FEC-derived SEI layer shows the lowest resistance value as the C-O species are less populated and salt decomposition is not serious. In short, the FEC-added electrolyte generates the SEI layer of the smallest resistance to give the best low-temperature performance for the graphite negative electrode.
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