자기-도핑형 p o l y ( PEGMA- c o -BF3LiMA) 전해질의 합성과 이온전도도에 대한 PEGMA분자량의 영향
Synthesis of Self-doped Poly(PEGMA-co-BF3LiMA)Electrolytes and Effect of PEGMA Molecular Weight on Ionic Conductivities
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분자량이 각각 300(PEGMA300) 및 1100(PEGMA1100) g mol−1 인 PEGMA와 합성된BF3LiMA 리튬염을 이용하여 다양한 조성의 고분자전해질을 제조하고 전기화학적 특성을 평가하였다. 흥미롭게도 AC-impedance 측정법에 의한 상온 이온전도도는 분자량 300gmol−1로 합성된 액체 고분자전해질에서 8.54 × 10−7Scm−1의 값이 얻어진 반면, PEGMA1100으로 합성된 고체상태의 고분자전해질에서 최대 14배 이상 높은 1.22 × 10−5Scm−1가 관찰되었다. 이러한 결과는 PEGMA에 ethylene oxide 단위가 5개인 300 g mol−1보다 23개인 1100gmol−1에서 리튬이온의 배위가 쉽게 일어나기 때문으로 해석된다. 또한 양이온 수율 측정결과 리튬메탈과 BF3간의 반응으로 인해 0.6의 비교적 낮은 값이 나왔지만 초기 3000초 동안에는 0.9 이상의 값이 관찰되어 단일이온 전도체의 특징을 보여주었다.
Abstract
Polymer electrolytes consisted of BF3LiMA and 300 (PEGMA300) or 1100(PEGMA1100) g mol−1 of PEGMA were prepared and the electrochemical properties were characterized. Interestingly, the AC-impedance measurement shows 1.22 × 10−5 S cm−1 of room temperature ionic conductivity from PEGMA1100 based solid polymer electrolytes while 8.54 ×10−7 S cm−1 was observed in PEGMA300 based liquid polymer electrolytes. The more suitable coordination between lithium ion and ethylene oxide (EO) unit might be the reason of higher ionic conductivity which can be possible in PEGMA1100 based electrolytes since it has 23EO units in monomer. The lithium ion transference number was found to be 0.6 due to the side reactions between BF3 and lithium metal expecially for longer time but 0.9 was observed
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