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研究生： 高培堯
Kao, Pei-Yao
論文名稱： Ca,Zr與Zn添加對鎂基負極材料組織與充放電特性研究
Effects of Adding Ca, Zr and Zn on Microstructure and Charge-Discharge Characteristics of Mg Alloy Anode Materials
指導教授： 洪飛義
Hung, Fei-Yi
呂傳盛
Lui, Truan-Sheng
學位類別： 碩士
Master
系所名稱： 工學院 - 材料科學及工程學系
Department of Materials Science and Engineering
論文出版年： 2019
畢業學年度： 107
語文別： 中文
論文頁數： 87
中文關鍵詞： 鎂電池 、鎂合金 、蒸鍍 、充放電 、負極
外文關鍵詞： Magnesium battery, Magnesium alloy, Thermal evaporation, Charge-discharge, Anode
相關次數： 點閱：63  下載：0 
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    • 隨著全球致力於推動電動汽機車等產業，其中儲能系統、智慧電網等亦相繼被討論，鋰離子電池作為上述應用的主要動力來源，金屬與合金負極材料相比於主流碳系材料具有更高的體積能量密度。本研究選用鎂作為電池負極材料，具有較高的理論電容量及低成本優勢，但在多次反應後因體積膨脹效應導致電池循環壽命不佳。基於此，本研究藉由添加鈣、鋯與鋅形成Mg-Ca、Mg-Zr及Mg-Zn合金，並以粉末塗佈法製備粉末電極，探討在形成金屬間化合物、非活性複合相與活性複合相三種不同機制下，對於體積膨脹效應的抑制效果及高溫環境下的充放電機制。此外，針對上述三者中循環表現最佳者，進一步以熱蒸鍍法製備薄膜電極，釐清相關材料本質之電化學反應機制，並評估Mg-C電池系統之可行性。
    實驗結果顯示，Mg-Ca合金中Mg2Ca能有效減緩循環充放電過程中鎂基地體積膨脹所導致的結構變形，而有最高的電容量與循環壽命。然而，Mg-Zr合金因首次循環中，電極表面固態電解質介面 (SEI)不易生成導致介面阻抗較高，鋰離子難以嵌脫使得電容量表現不佳，而Mg-Zn合金以不同反應電位的活性相來降低反應速率，對減緩充放體積膨脹的效果相對不佳。利用熱蒸鍍法所製備的Mg-Ca薄膜電極在無添加導電材料與黏合劑的情形下，活性材料佔比高，並有較大的反應表面積，使得電極材料能高度鋰化，大幅提升電容量。此外，大量鋰離子嵌脫也放大體積膨脹效應，使得55oC高溫下電極微觀組織呈現破碎形貌，當溫度升至85oC時，電極更將大幅劣化而失效。由循環伏安 (CV)分析結果可知高溫充放有助於SEI層生成，並且透過交流阻抗分析 (EIS)確認該SEI層能降低電極與電解質介面阻抗，提高鋰離子對電極材料的嵌入數目。最後，本研究將Mg-Ca薄膜電極導入Mg-C電池系統，發現在不同溫度下 (25/55oC)保有250-350 mAh/g的電容量，確立Mg-C電池系統的工業應用可行性。

    In recent years, electric vehicles have become popular, and lithium-ion batteries have been the main driving force for the above applications. Magnesium as an anode material has a high theoretical capacity and low cost, but the cycle life is poor due to the volume expansion effect. Based on this, this study compared the charge-discharge performance and cycle stability of Mg-Ca, Mg-Zr and Mg-Zn alloy electrodes at different temperatures. In addition, a Mg-Ca thin film electrode is prepared by thermal evaporation, and its electrochemical reaction mechanism was discussed. The results show that the Mg2Ca phase in the Mg-Ca alloy can effectively alleviate the structural deformation caused by the volume expansion of the magnesium base during cyclic charging and discharging, and has the highest capacity and good cycle life. However, due to the unstable formation of the solid electrolyte interface (SEI) on the Mg-Zr alloy electrode surface during the first cycle, the interface impedance is high and lithium ions are difficult to insert. The effect of the Mg-Zn alloy electrode using different reaction potentials of different active phases to slow down the volume expansion ratio is relatively poor. The Mg-Ca thin film electrode prepared by the thermal evaporation method has a high proportion of active materials, so that the electrode has higher capacity. From the results of cyclic voltammetry (CV), it is known that high temperature contributes to the formation of the SEI layer, and it is confirmed by electrochemical impedance spectroscopy (EIS) that the SEI layer can reduce the electrode-electrolyte interface impedance and improve lithium ion conductivity. Finally, this study imports the Mg-Ca thin film electrode into the Mg-C battery system and show that it has a capacity of 250-350 mAh/g at different temperatures (25/55°C), indicating that the magnesium battery has industrial application feasibility.

    中文摘要 I 英文摘要 III 致謝 XX 總目錄 XXII 圖目錄 XXV 表目錄 XXIX 第一章 前言 1 第二章 文獻回顧 3 2-1 鋰離子二次電池與工作原理 3 2-2 鋰離子電池之負極材料 3 2-3 鎂基負極材料 5 2-4 鎂-鈣、鎂-鋯、鎂-鋅負極材料 6 2-4-1 鎂-鈣合金 6 2-4-2 鎂-鋯合金 6 2-4-3 鎂-鋅合金 7 2-5 電極製程 7 2-5-1 混漿塗佈粉末電極製程 7 2-5-2 熱蒸鍍薄膜電極製程 8 2-5-3 濺鍍薄膜電極製程 8 2-6 高溫充放電機制 9 2-7 研究目的 9 第三章 實驗步驟與方法 16 3-1 實驗流程概述 16 3-2 實驗粉末與電極製備 16 3-2-1 混漿塗佈電極製備 17 3-2-2 熱蒸鍍電極製備 17 3-3 電極材料微觀組織分析 18 3-3-1 低掠角X-ray繞射分析 18 3-3-2 掃描式電子顯微鏡與EDS分析 18 3-4 電池組裝與測試 18 3-4-1 充放電測試 19 3-4-2 循環伏安分析 19 3-4-3 電化學阻抗分析 19 3-4-4 傅立葉轉換紅外線光譜分析 20 第四章 結果與討論 26 4-1 鎂-鈣、鎂-鋯、鎂-鋅合金粉末塗佈電極特性 26 4-1-1 鎂合金粉末電極微觀結構與元素成分分析 26 4-1-2 鎂合金粉末電極充放電循環特性 26 4-1-3 鎂合金粉末電極X-ray繞射分析 29 4-1-4 鎂合金粉末電極循環伏安分析 30 4-1-5 鎂合金粉末電極交流阻抗分析 33 4-2 熱蒸鍍鎂-鈣薄膜電極特性 34 4-2-1 鎂-鈣薄膜電極微觀結構與元素成分分析 34 4-2-2 鎂-鈣薄膜電極充放電循環特性 35 4-2-3 鎂-鈣薄膜電極X-ray繞射分析 37 4-2-4 鎂-鈣薄膜電極循環伏安分析 37 4-2-5 鎂-鈣薄膜電極交流阻抗分析 39 4-2-6 鎂-鈣薄膜電極FTIR光學結構分析 39 4-3 鎂-鈣電極充放電機制探討 40 第五章 結論 81 參考文獻 82

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