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研究生: 廖譽凱
Liao, Yu-Kai
論文名稱: 石榴石型全固態電解質電池製作及其特性分析
Preparation and Characterization of Garnet-type All Solid State Electrolyte Batteries
指導教授: 胡淑芬
Hu, Shu-Fen
學位類別: 碩士
Master
系所名稱: 物理學系
Department of Physics
論文出版年: 2018
畢業學年度: 106
語文別: 中文
論文頁數: 66
中文關鍵詞: 全固態電池鋰鑭鋯氧界面層
英文關鍵詞: All solid state batteries, LLZO, interfacial layer
DOI URL: http://doi.org/10.6345/THE.NTNU.DP.018.2018.B04
論文種類: 學術論文
相關次數: 點閱:220下載:3
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  • 科技發展日新月累,人們對科技產品要求與日俱增,儲能系統為新世代科技產品之命脈,其中電池為最重要與常見之儲能系統。現今商用鋰離子電池多使用膠態與液態電解質具充放電前後不可逆電容高與爆炸之問題。三星Galaxy Note7因手機電池隔離膜過薄,且電池設計不良使電極受擠壓接觸短路,造成多起爆炸事件後,安全性於鋰離子電池研究中躍至首席地位。故本研究藉固態電解質取代傳統液態與膠態電解質,固態電解質具高安全性、高能量密度等優點。
    研究第一部分以固態反應法合成固態電解質鋰鑭鋯氧 (Li7La3Zr2O12; LLZO)、鋰鑭鋯鉭氧 (Li6.75La3Zr1.75Ta0.25O12; LLZTO)與鋰鎵鑭鋯鉭氧(Li6.8Ba0.05La2.95Zr1.75Ta0.25O12; LBLZTO)做比較,證明經元素摻雜後提升固態電解質離子導電度,並以鋰金屬與磷酸鋰鐵複合式正極組合全固態電池,元素摻雜前首圈放電電容為45 mAh g-1,經鉭與鋇摻雜後提升至150 mAh g-1。研究第二部分因全固態電池微觀表面接觸性不佳與鋰枝晶問題,故於界面處藉以高分子界面膜提升其表面接觸性。經電化學阻抗量測各系列界面阻抗,證明高分子界面膜使界面電阻以1309至388 Ω cm2。

    The goal of this study is to fabricate and analyze all-solid-state Li-ion battery interface, thereby enhancing the Cycling stability. The cell assembled by highly conductivity garnet-type solid-state electrolyte (SSE)Li7La3Zr2O12 (LLZO), Li6.75La3Zr1.75Ta0.25O12 (LLZTO) and Li6.8Ba0.05La2.95Zr1.75Ta0.25O12 (LBLZTO). The cathode slurry was prepared by mixing poly(vinylidene fluoride) (PVdF), LiTFSI , KS6 and LiFePO4 and directly coating on SSE one side. Li-foil was pressed on the opposite side as an anode. The interface between cathode and SSE was filled by PEO : LiTFSI (1:1) which acts as a buffer layer to minimize interface resistance. Specific capacity and cycle life test were carried out at a rate of 0.05 C. Conductivity of the SSEs are in the order of 10-4 S/cm at room temperature as obtained from electrochemical impedance spectroscopy (EIS). The cell was cycled at 60°C for 15 repeated cycles. The first cycle charge capacity of the cell is 45, 140 and 150 mAhg-1.
    The formation of Li-SSE interfacial contact has been inhibited using a buffer layer with Li-ion containing polymer layer(PEO : LiTFSI = 1 : 1) and reduce interface resistance between SSE and cathode form 1309 to 388 Ω cm2.

    謝辭 I 摘要 II Abstract III 目錄 IV 圖目錄 VII 第一章 緒論 1 1.1 電池之起源 2 1.2 鋰離子二次電池 4 1.3 鋰離子電池正極材料 5 1.3.1 嵌入式正極 5 1.3.1.1 層狀正極材料 5 1.3.1.2 尖晶石型正極材料 7 1.3.1.3 橄欖石型正極材料 9 1.3.2 反應式正極 9 1.4 固態電解質相間界面(solid electrolyte interphase; SEI) 12 1.5 鋰離子電池負極材料 13 1.5.1 鋰金屬 13 1.5.2 碳材 14 1.5.3 矽負極 15 1.5.4 鈦酸鋰(lithium titanium oxide; Li4Ti5O12) 17 1.6 鋰離子電池電解質 17 1.6.1 液態電解質 17 1.6.2 膠態電解質 18 1.6.3 無機固態電解質 18 1.6.4 鋰鑭鋯氧(Li6.75La3Zr2O12; LLZO) 20 1.7 固態電解質界面改善 23 1.8 研究動機與目的 24 第二章 實驗步驟與儀器分析原理 25 2.1 化學藥品 25 2.2 摻雜元素之鋰鑭鋯氧合成實驗步驟 26 2.3 全固態電池 27 2.3.1 複合正極 27 2.3.2 全固態電池組裝 28 2.3.3 高分子膠態界面層 28 2.4 分析儀器與原理 29 2.4.1 X 光繞射儀(X-ray diffraction; XRD) 29 2.4.1.1 同步輻射光源 (synchrotron radiation light source) 30 2.4.1.2 結構精算圖 (refinement)[45] 32 2.4.2 X光吸收光譜(X-ray absorption spectroscopy; XAS ) 33 2.4.2.1 X光近邊緣吸收光譜(X-ray absorption near edge spectroscopy; XANES) 35 2.4.2.2 延伸X光吸收微結構(Extended X-ray absorption fine structure; EXAFS) 36 2.4.3 X光光電子能譜(X-ray photoelectron spectroscopy; XPS ) 37 2.4.4 掃描式電子顯微鏡(scanning electron microscope; SEM ) 38 2.4.5 固態核磁共振儀(solid state nuclear magnetic resonance; SSNMR ) 39 2.4.6 電化學阻抗譜(electrical impedance spectroscopy; EIS) 42 2.4.7 阿瑞尼士圖(Arrhenius plot) 43 2.4.8 充放電測試儀(cycling test machine) 44 第三章 結果與討論 46 3.1 LLZO、LLZTO與LBLZTO結構分析 46 3.1.1 X光繞射 46 3.1.2 中子粉末繞射 47 3.1.3 X光吸收光譜比較 52 3.1.4 掃描式電子顯微鏡鑑定 52 3.2 多元素摻雜之鋰鑭鋯氧電化學分析 54 3.2.1 交流阻抗測試 54 3.2.2 阿瑞尼士圖分析 55 3.2.3 鋰7固態核磁共振分析 56 3.2.4 全固態電池充放電測試 57 3.2.5 界面保護層 59 第四章 結論 62 參考文獻 63

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