本論文之研究首先通過同步輻射加速器X射線衍射和穿透式電子顯微鏡研究在鋰化/脫鋰化過程中電極材料的結構變化與循環壽命的影響，了解到石墨的非晶化源自周期性體積變化引起的內部應力累積，從而導致強度和韌性降低，同樣的現象在矽更加明顯，之後提出了一種新型的摻氮導電超奈米微晶鑽石塗層（N-UNCD），通過微波等離子增強化學氣相沉積（MPCVD）塗覆在天然石墨（NG）和奈米矽表面，與原始的石墨和原始的奈米矽相比，N-UNCD塗覆的石墨負極和N-UNCD塗覆的奈米矽負極展顯出更優異的循環壽命、快速充放電能力以及有效降低第一圈不可逆電量。N-UNCD膜具有高楊氏係數、高化學穩定性以及高導電性，改善了在充電/放電過程的連續體積變化破壞、更穩定的固態電解質介面(SEI)以及增加奈米矽的導電性。

The aim of this research is to investigate the structural changes and degradation of electrode materials during intercalation/deintercalation leading to reversible capacity loss and short cycle life have plagued LIB from advancing forward. In order to overcome these hurdles, a novel conducting nitrogen-incorporated ultrananocrystalline diamond (N-UNCD) is proposed to coat on the natural graphite (NG) and nano silicon by microwave plasma-enhanced chemical vapor deposition (MPCVD), demonstrating the superior improvement on electrode stability. The electrochemical results of the N-UNCD coated NG anode and N-UNCD coated nano silicon reveal excellent cyclability, rate capability and conductivity over a hundred cycles as compared to the pristine NG and pristine nano silicon. Furthermore, the underlying high structural stability of the N-UNCD coating for the anode material and the failure mechanism of the pristine NG anode is fully elucidated by combining diffraction and imaging techniques based on in-situ synchrotron X-ray diffraction and high-resolution transmission electron microscopy. These results show that the amorphization of NG originates from the accumulation of internal stress by periodic volume changes, which leads to mechanical fading with loss of strength and toughness. However, the N-UNCD film serves as a strong buffer layer to accommodate the volume changes, and also maintains the mechanical integrity of the pristine anode by suppressing from the continuous damage and the thickening of the solid electrolyte interphase during charging/discharging. Optimally, our investigations systematically explain the failure mechanism of the pristine anode, and shed a light on constructing a high capability and long cycle N-UNCD coated anode for LIBs.

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