近年來鋰離子電池被視為最具潛力的能源電池，具有工作電壓高、能量密度大、循環受命長等特點。為促進鋰離子電池在電動車上的應用普及化，如何有效地改善其安全性能為一大關鍵，廣泛且具有經濟效益的解決方法為電解液添加劑的使用。本研究著重於探討具有聚合性質之成膜添加劑的還原反應機制及性質，成膜添加劑能夠在首次充放電下，於碳極表面發生自由基/陰離子聚合反應，先行還原分解，並先成一具有良好穩定性的固體電解質界面膜 (SEI)，有效抑制溶劑分子於碳極還原，因而避免產生損害電極之中間產物和氣體，並遏止鋰離子溶劑化合物 (Li+(S)n ,S = solvent, n = 1~4)嵌入碳極所造成的電極崩解。
為闡明添加劑2-氰基呋喃(2-cyanofuran, 2CF)在碳酸丙烯酯 (Propylene carbonate, PC)電解液形成SEI膜的電化學聚合反應機制，本研究使用密度泛函理論中的B3LYP方法，以6-311++G**為基組，在考慮溶劑體系下，進行成膜添加劑2CF的模擬分析，探討其在單電子與雙電子還原分解的動力學與熱力學性質。計算結果顯示2CF傾向雙電子還原分解反應，還原後主要進行CN-分離與開環二反應路徑，有效地於碳極表面還原分解、聚合，進而抑制溶劑的共嵌入反應。
第二部份考慮鋰鹽在電解液系統中對添加劑還原分解機制的影響。鋰離子和添加劑分子於電解液中形成一離子添加劑化合物((CFn-)Li+，n = 1~2)，計算結果指出2CF還原產生陰離子自由基2CF-，再與鋰離子反應形成(CF-)Li+。相對於(PC)-Li+，(CF-)Li+具有較高之電子親和力((CF-)-Li+ vs. (PC)-Li+ = 1.67 vs. 1.07 eV)，顯示(CF-)Li+較(PC)-Li+容易進行還原反應而產生(CF2-)-Li+分子，而後再進行分解或聚合。由反應動力學與熱力學性質歸納出Li-CN分離為最容易發生之反應路徑，產生之反應中間體furanide anion，可經由攻擊2CF單體形成聚合中間體，進行陰離子加成聚合反應。
本研究詳細探討2CF的還原、分解及聚合機制，證明2CF能夠有效形成穩定SEI膜，預期可以改善鋰離子電池性能。

Lithium ion battery is thought as a promising power source for its high voltage, high cycle performance and high energy densities. The increase in improvement of safety is a key point for commercialization of lithium-ion batteries in the auto-mobile application. Using electrolyte additives is one of the most economic methods to enhance the performance of Lithium-ion batteries. In this contribution, we focus on reduction type additives which are reported to form electrochemically polymerizable intermediates. The reduction products assist in the formation of a stable solid electrolyte interface at the anode surface.
To elucidate the mechanism of electrochemical polymerization of 2-Cyanofuran in Propylene Carbonate (PC) based electrolyte for Lithium-ion batteries, the electrochemical reduction of 2-Cyanofuran is investigated by using density functional theory (DFT) at B3LYP/6-311 ++ G** level. Based on theoretical calculation, one and two electrons reduction have been comprehensively analyzed. 2-Cyanofuran undergoes two electrons reduction more feasibly than one electron reduction and efficiently suppresses the decomposition of PC. Regarding the two electrons decomposition mechanisms, the 2-cyanofuran anion undergoes through elimination of the cyano group and ring opening channel. The salt effects is incorporated with the clusters (CF n-)-Li+ (n=1-2). From calculated results, the presence of Li+ considerably stabilizes the 2CF anion to form a more stable ion-pair intermediate, which proceeds through a subsequent reduction to give in (CF2-)-Li+ with a higher electron affinity than PC. Elimination of the lithium cyanide anion of (CF2-)-Li+ results in formation of α-carbene anion which leads to subsequent polymerization via nucleophilic attack on 2-Cyanofuran monomer. The ring opening leads to following decomposition reactions resulting polymerizable intermediates. This work gives detailed investigation about the reduction path of 2-Cyanofuran which contributes to the formation of a stable solid electrolyte interphase.

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