人類隨著科技發展，能源需求逐漸增加，現今社會對於其開發及效能提升也越來越重視，在眾多電能儲存技術方面，鋰電池扮演著舉足輕重的角色，也是持續在研發中的能源。在鋰電池運作的過程中，金屬氧化物晶格表面的電子傳遞行為是相當重要的一環，為此，許多實驗以及理論計算的研究人員不遺餘力的進行開發，以提升鋰電池的效能。
本論文使用密度泛函理論（Density Functional Theory, DFT）研究電解液在陰極表面的吸附及分解機制，了解可以提升電池的穩定性、電容量以及循環使用次數的原因。我們使用第一原理（Ab-initio）方法，計算碳酸乙烯酯（Ethylene Carbonate, EC）在完全放電後的尖晶石結構LiMn2O4（100）催化表面上的吸附及分解機制，利用GGA+U的計算方法，找到六種EC在LiMn2O4（100）表面的吸附模式，利用態密度（Density of States, DOS）、投影態密度（Project Density of States, PDOS）以及電荷密度差（Electron Density Difference, EDD）比較其吸附前後的電子傳遞方向；在分解反應中，利用Climbing Image Nudged Elastic Band （CINEB）的方法搜尋過渡態。分析結果顯示，在所有考慮的吸附模式中，電子傳遞的方向皆是由表面傳遞至EC，使其產生自由基進而斷碳氧鍵開環，並且，在分解反應的過程中，不會產生氣體。

A need for improved and efficient energy storage technology is pragmatic for the sustainable development of our society. With this respect, the development of electrochemical energy storage technologies, such as lithium ion batteries, will play a grand role in the advancement of alternative renewable energy sources. Such battery technologies employ redox reactions with intercalation reactions in crystalline metal oxides, where lithium ions act as charge carriers to produce efficient and high power energy storage options. Therefore, a comprehensive understanding of the important processes occurring in lithium ion battery by using either computational or experimental approach will help to develop batteries with better performance.
The adsorption and decomposition mechanism of electrolyte on the cathode surface is one of the governing factors which control the stability, capacity and cyclic life. In this thesis, first principles calculations are used to study the adsorption and surface catalyzed decomposition mechanisms of ethylene carbonate on the (100) surface of fully discharged LiMn2O4. Six different adsorption configuration of EC on LiMn2O4 (100) surface was found by using GGA+U approximation. The adsorption strength and electronic properties of each site was then discussed by using density of states (DOS), projected density of states (PDOS) and electron density difference (EDD). Moreover, the initial decomposition mechanisms of EC on LiMn2O4 (100) surface is investigated by examining the minimum energy path between these two minima using the climbing image nudged elastic band reaction-pathway sampling scheme. In all sites, an electron transfer from the surface to the adsorbate was observed resulting in weakening and subsequent breaking of C-O bond and formation of open chain radical. Even though adsorption and decomposition reaction can occur on the (100) surface of LiMn2O4, for all configurations studied, the results show that the generation of gas is highly unlikely to occur at normal condition. In order to investigate the catalytic effect of the surface on the EC decomposition reaction, DFT calculations for the gas phase molecular decomposition of EC are performed and discussed in detail. In general, this work aims to give an insight about the initial stages in surface catalyzed electrolyte decomposition reactions on spinel cathode structure.

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