透過電解質還原反應，在陽極表面形成之固體電解質膜(SEI)，是影響鋰離子電池性能的重要因素之一。在電解質組成中，鋰鹽對於在陽極表面上所形成的SEI扮演著非常重要的角色。目前，六氟磷酸鋰（LiPF6）是鋰離子電池中唯一在商業上使用的鋰鹽，因為它具有高溶解性，高離子傳導性和相對便宜的價格。然而，LiPF6經歷自催化分解並產生HF和POF，使它的熱穩定性和化學穩定性受到限制，這都間接導致了鋰電池的安全憂慮。最近我們實驗室開發了一種新型苯並咪唑基鹽類，它具有優於LiPF6的電化學性能，包括雙（三氟硼烷）-5-腈基-2-（三氟甲基）苯並咪唑鋰（LiBTCTB），雙（三氟硼烷）-5-硝基-2鋰 - （三氟甲基）苯並咪唑鋰（LiBTNTB）和雙（三氟硼烷）-2-（三氟甲基）苯並咪唑啉鋰（LiBTTB）。在此研究中，使用分子動力學（AIMD）模擬了這三種新型苯並咪唑基鹽和LiPF6所形成的SEI層來研究分析比較。為了更深入了解這些系統中的SEI層，我們主要研究電解質-鋰電極之界面反應，包括由不同鋰鹽及碳酸亞乙酯（EC）和碳酸二乙酯(DEC）所組成的雙溶劑混合物電解質所發生的分解反應。我們首先發現LiPF6在陽極表面上完全分解並形成LiF。此外，觀察到溶劑EC的反應機制包括了開環及其分解。並對不同苯並咪唑基鋰鹽的反應性與LiPF6進行比較，我們發現LiBTCTB在與鋰電極表面接觸時反應非常快，且與LiPF6相比能更快速的形成SEI層。我們還發現LiBTCTB抑制了溶劑分解，而且LiBTNTB減少了陽極表面上溶劑的分解數量。此外，我們建構了由LiPF6和LiBTCTB與EC和DEC組成的雙鋰鹽系統電解質，且發現了雙鋰鹽系統增加了鋰電極表面上電解質的穩定性，從而改善了SEI層的形成。此外，透過研究過量電子環境對於LiPF6/EC/DEC混合物中SEI層形成的影響，我們的結果表明過量電子的存在引導了電解質分解並在陽極表面上更快地形成SEI層。基於這些理論計算結果，我們預計LiBTCTB將成為下一代鋰離子電池的潛力鋰鹽。

The solid-electrolyte interphase (SEI) layers formation at the anode surface through the reductive decomposition of the electrolyte components is one of the important factors that affect the Lithium-ion battery performance. Among the electrolyte components, the lithium salt has a vital role in the structure of the SEI formed on the anode surface. Presently lithium hexafluorophosphate (LiPF6) is the only commercially utilized lithium salt in the lithium-ion batteries because of its high solubility, high ionic conductivity, and relatively low price. However, thermal and chemical stability of LiPF6 is limited, and it undergoes autocatalytic decomposition and yield HF and POF, which leads to a safety hazard. More recently, our group have developed a novel benzimidazole based salts with superior electrochemical properties to LiPF6 including lithium bis(trifluoroborane)-5-cyano-2-(trifluoromethyl) benzimidazolide (LiBTCTB), lithium bis(trifluoroborane)-5-nitro-2-(trifluoromethyl) benzimidazolide (LiBTNTB), and lithium bis(trifluoroborane)-2-(trifluoromethyl) benzimidazolide (LiBTTB). In this study, a comparative investigation of these three novel benzimidazole based salts and LiPF6 on the formation of the SEI layer has been carried out using ab initio molecular dynamics (AIMD) simulations. To gain insight into SEI formation in these systems, we mainly investigate the interfacial reactions such as decomposition of electrolyte consisting of the different Li salt and the binary solvent mixture ethylene carbonate (EC) and diethyl carbonate (DEC) occurring at the lithium anode surface. We first find that the LiPF6 salt fully decomposed and formed LiF
on the anode surface. Also, the solvent EC reaction mechanisms, including EC ring opening and its decomposition are observed. The reactivity of different benzimidazole based Li salts are compared with LiPF6 salt, and we find that the LiBTCTB salt reacts very fast when in contact with the Li anode surface and forms SEI layer quickly compared to LiPF6. It is also found that LiBTCTB salt inhibits the solvent decomposition and LiBTNTB minimizes the solvent decomposition on the anode surface. We also construct the electrolyte consisting of dual salts LiPF6 and LiBTCTB with EC and DEC mixture and find that dual salt increased the stability of electrolyte on the Li anode surface and thereby improve SEI formation. In addition, we have investigated the effects of excess electrons on the SEI formation in LiPF6/EC/DEC mixture, and our results demonstrate that the presence of excess electrons induces the electrolyte decomposition and forms the SEI layer faster on the anode surface. Based on these theoretical results, we expect that the LiBTCTB salt will be the potential Li salt for the next generation of Li-ion batteries.

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