本研究針對過量鋰正極材料Li[Li0.2Ni0.2Mn0.6]O2及奈米矽碳負極材料等高電容量先進電極材料進行結構衰退機制及電化學效能分析之研究。針對過量鋰正極材料Li[Li0.2Ni0.2Mn0.6]O2之結構衰退與效能善，研究中藉由晶體結構及表面結構分析方法建立Li[Li0.2Ni0.2Mn0.6]O2過量鋰正極材料結構鑑定程序及萃取細部分析資訊，並由高溫(80 ℃)、高濕(RH 100%)老化實驗得知，Li[Li0.2Ni0.2Mn0.6]O2過量鋰正極材料結構表面的鋰離子易與環境中的水氣及CO2產生反應形成LiOH及Li2CO3沉積，經Raman及XPS分析結果顯示，隨著老化時間的增長，將導致表面結構的老化及沉積物的增加，造成電化學效能的劣化。另以Raman光譜及Soft XAS吸收光譜，針對不同充電截止電壓之充放電策略下的表面結構衰變及電子結構的變化進行分析，經300圈充放電循環測試後可觀察到表面層狀至尖晶狀結構的轉變與錳、氧離子的電子結構變化，由分析結果得知，全程限定4.6 V充電截止電壓可減緩氧活化平台造成的負面影響 (如結構的活化重構、晶格空缺的損耗及結構的扭曲)，使電化學循環穩定度獲得改善。對於奈米矽碳負極材料的效能提升與電極結構崩壞抑制，研究中利用靜電吸附自組裝及水熱法雙重碳塗覆程序之策略，發展出具有yolk-shell結構之矽/還原石墨烯氧化物/無定形碳(YS-Si@rGO/a-C)負極材料，所建構之rGO/a-C複合緩衝層不僅能形成3D電子傳遞網路，並具有良好的緩衝彈性，搭配優勢的預置空間，則可承受矽奈米粒子體積膨脹的應力變化，穩定SEI的生成，維持電極結構的完整性，表現出良好的電化學循環效能及電容量穩定性，經101圈充放電循環後，仍可維持1249 mAh/g之電容量，75 %電容量維持率，而低rGO含量的控制，可降低SEI的生成面積，提升可逆電容量的貢獻，獲得76 %的第一圈庫倫效率，1668 mAh/g的第一圈可逆電容量。
由全電池模組充放電驗證結果得知，以Li[Li0.2Ni0.2Mn0.6]O2過量鋰正極與YS-Si@rGO/a-C負極所建立的全電池模組具有達3.3 V的工作電壓及213 mAh/g的可逆電容量，其能量密度的貢獻皆大於一般典型的商售電池系統(如LiCoO2/MCMB、LiFePO4/MCMB)，而4.8 V高工作截止電壓除引發Li[Li0.2Ni0.2Mn0.6]O2結構的衰變外，電解液的催化裂解，亦會促使YS-Si@rGO/a-C負極端SEI的大量生成，造成電容量及電壓平台的快速衰退，而限定4.6 V充電截止電壓之充放電策略則可減緩電容量快速衰退的情形，提升電化學效能穩定性。

In this study, the mechanisms of structural deterioration and enhancement of electrochemical performance for high-energy advanced lithium ion batteries materials, including Li-rich Li[Li0.2Ni0.2Mn0.6]O2 cathode material and nanostructured Si/C anode material, are investigated. In the issues of structural deterioration and performance improving for Li-rich layered cathode material, the identification process and detail structural information of Li1.2Ni0.2Mn0.6O2 cathode material were confirmed by series phase identification of crystal structure and surface structure analysis. Furthermore, under hot (80 oC) and humid (RH 100%) aging process, the Li-ion on the surface of Li-rich Li[Li0.2Ni0.2Mn0.6]O2 cathode material is prone to react with H2O and CO2 in air and form LiOH and Li2CO3. An increased in surface aged structure and deposition layer as the increased in aging time was evidenced by Raman and XPS analysis, which results in the degradation of the electrochemical performance. Additionally, the surface structure decline and electronic structure evolution for Li1.2Ni0.2Mn0.6O2 cathode material in various cycling protocols were investigated by Raman spectroscopy and soft XAS absorption spectroscopy, the changes for surface layered-to-spinel phase transformation and electronic structure variation of manganese and oxygen ions were observed after 300 cycles. As the results, the protocol of overall restricted 4.6 V charge cut-off voltages could reduce the adverse effects, including the structural reconstruction, the loss of vacancy or hole in lattice and structural distortion, during the oxygen plateau and thus improving the electrochemical cycling stability. In order to improve the electrochemical performance and mitigate the electrode pulverization, an effective strategy based on the synergistic dual-coating process of electrostatic self-assembly and the hydrothermal carbonization of glucose to produce a unique yolk-shell structured rGO/silicon/amorphous carbon (a-C) anode material (YS-Si@ rGO/a-C). The rGO/a-C composite shell of YS-Si@rGO/a-C anode prepared by the developed dual coating process not only confers a 3D electronic conductive network, the strong-integration of rGO and a-C makes the composite rGO/a-C shell more resilient. The incorporated buffer space and rGO/a-C shell give a synergetic effect to help YS-Si@rGO/a-C anode endure the stress changes due to the large volume expansions, while at the same time allowing the formation of a stable SEI on the surface of the electrode, maintaining the structural integrity of electrode during cycling. The overall yolk-shell structure results in good rate capability and better cyclability. As a result, the composite anode exhibits stable capacity retention of 75 % after over 100 cycles, a reversible capacity of 1249 mAh/g at 101 cycles. Meanwhile, the initial reversible capacity ratio of 76 %, a high reversible capacity 1668 mAh/g at the 1st cycle were achieved by limited loading of high-surface-area rGO.
In the full cell system of Li[Li0.2Ni0.2Mn0.6]O2 cathode /YS-Si@rGO/a-C anode, the remarkable potential window of 3.3 V and reversible capacity of 213 mAh/g deliver higher energy density than other conventional Li-ion batteries (LiCoO2/MCMB, LiFePO4/MCMB). However, a high cut-off voltage of 4.8 V causes the severe voltage decay and fast capacity fading due to the structural deterioration of Li[Li0.2Ni0.2Mn0.6]O2 cathode, electrolyte decomposition and thickening the SEI formation of YS-Si@rGO/a-C anode. Such adverse effects during the high working voltage of 4.8 V were mitigated by restricting the cut-off voltage of 4.6 V, improving the electrochemical cyclability.

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