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研究生: 吳仁淵
Wu, Jen-Yuan
論文名稱: 探討Li3PO4水性離子導體之添加增進單質硫鋰電池高速率充放電性能之研究
Investigation of Electrochemical Performance of Lithium-Sulfur Cell with High C-Rate Capability by Addition of Water-Soluble Li3PO4 Ionic Conductor
指導教授: 蔡哲正
口試委員: 林居南
顏光甫
學位類別: 碩士
Master
系所名稱: 工學院 - 材料科學工程學系
Materials Science and Engineering
論文出版年: 2014
畢業學年度: 102
語文別: 中文
論文頁數: 66
中文關鍵詞: 鋰硫電池高速率充放電離子導體
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  • 由於鋰硫電池在充放電過程的硫分子斷鍵與生成的可反應鋰離子量不受到晶體結構的受限,因此具備1673 mAh/g的理論電容量,遠高於嵌入結構型鋰離子電池的5倍之多,為次世代在高載能儲能系統中的開發重點材料之ㄧ。本研究中以LiNO3作為共鋰鹽類探討液態型鋰硫電池的反應機制,研究發現其電解液添加量與充放電中的截停電位(cut-off voltage)分別影響了初期放電容量與後期循環壽命表現,當中以E/S比值在20 ml/g並以1.7-2.8 V電位區間充放電為本研究中的最佳化參數。另外,本研究首次以簡單製程方法將水性Li3PO4離子導體導入系統中,從循環伏安法中可發現,當含量達到導電添加劑的25 %量時可得到最佳的氧化還原的可逆性。以交流阻抗與X-ray結晶性分析中發現在充放電後的硫分子具有相對較低的電荷傳導阻抗及結晶性,另外從SEM分析中顯示,由於25 % Li3PO4的添加量其在材料表面基底(Matrix)上能均勻散布500-700 nm顆粒,不僅能降低鋰離子與活性物質界面間的電荷轉移阻抗,還能作為硫分子在氧化還原中形成多硫化物後再析出的附著載體,使得在高變速率循環壽命上有最佳的表現。


    Rechargeable lithium sulfur cell has become the next-generation energy storage system owing to its theoretical capacity of 1673 mAh/g is 5 times higher than current state of layer-like lithium ion cell based on intercalation mechanism. The discharge/charge of electrode is formed with cleavage/formation, therefore its quantity of reactive lithium ions are not constrained by the structural stability.The present work attempts to study the characteristics of liquid-based lithium sulfur cell with lithium co-salt of LiNO3. At the first part, the study examines how the cut-off voltage region and addition of electrolyte volume (E/S ratio) affect the earlier stage of discharge capacity and middle/later stage of cycle retention. At the second part, water soluble Li3PO4 of ionic conductor is introduced to the lithium sulfur system. The study compares the electrochemical performance by using cycle voltammetry method, AC impedance method, X-ray diffraction and SEM analysis. The results suggest that the addition of 16.7 to 25 % Li3PO4 of conductive agent shows the uniform distribution on the electrode after charge/discharge, therefore they have better rate capability and cycle performance. Such a simple method for the construction of electrode scaffolds shows potential for high C-rate performance lithium sulfur batteries.



    目錄 中文摘要 I Abstract II 致謝 III 目錄 IV 圖目錄 VI 表目錄 IX 第一章 緒論 1 第二章 文獻回顧 5 2-1塊狀硫的生成(Bottom-up process) 5 2-2硫與鋰的基本特性 7 2-2.1 硫 7 2-2.2金屬鋰 7 2-3鋰-含硫系電池(Lithium-Sulfur containing batteries) 8 2-3.1無機二硫化物系統 8 2-3.2 有機(聚)硫化物系統 9 2-3.3 單質硫系統 10 2-4充電/放電原理與機制 11 2-5影響電池性能的因素 13 2-5.1 陰極複合層活物/生成物不均勻析出 13 2-5.2氧化還原梭現象 14 2-6 液態電解質系統 15 2-7抑制多硫化鏈的研究 17 2-7.1 奈米級複合材料 17 2-7.2 蛋(核)殼(Yolk(core)-shell)結構 18 2-7.3 碳材阻隔層 18 2-7.4 電解液添加劑 20 2-7.5 電解質聚合物 21 2-7.6 氧化物/中孔碳複合材料 22 2-8研究目的 24 第三章實驗技術與原理 25 3-1實驗藥品 25 3-2材料製備 26 3-2.1 Weimarn-型塊狀硫 26 3-2.2 Li3PO4製備 26 3-3電極製備 26 3-4 電池組裝 27 3-5 材料分析 30 3-5.1 場發式顯微鏡 30 3-5.2 X-ray晶體繞射 30 3-6 循環伏安法 31 3-6.1原理 31 3-6.2 量測參數 32 3-7 交流阻抗分析儀 33 3.7.1 原理 33 3.7.2 等相位角元件(Constant phase element) 33 3-7.3量測參數 34 第四章結果與討論 35 4-1 材料微觀形貌 35 4-1.1 Weimarn析出硫 35 4-1.2 Li3PO4的生成 37 4-2 電池參數最佳化 39 4-2.1 截停充放電壓 39 4-2.2電解液體積量與活性物質重量比的影響 42 4-3極片微觀形貌與結晶分析 45 4-4 循環伏安量測 48 4-5循環壽命測試 51 4-6 交流阻抗量測 54 4-7 充放電後結晶分析與表面形貌 56 第五章 結論與未來展望 60 參考文獻 61 附錄ㄧ 65 附錄二 66

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