利用吡咯烷離子液體修飾鋰離子電池之 Li7La3Zr2O12 基固態電解質與鋰金屬電極界面

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林與絜(Yu-chieh Lin) 查詢紙本館藏

畢業系所

材料科學與工程研究所

論文名稱

利用吡咯烷離子液體修飾鋰離子電池之 Li7La3Zr2O12 基固態電解質與鋰金屬電極界面
(Modification of Li7La3Zr2O7-Based Solid Electrolyte and Li Electrode Interface Using Pyrrolidinium Ionic Liquid for Li-ion Battery)

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摘要(中)

本研究採用熱壓方式製備 Li6.75La3Zr1.75Ta0.25O12 (LLZTO)陶瓷電解質，並且利用離子液體(LiFSI/PMPFSI)作為修飾劑，形成富含 LiF 且穩定的固態電解質界面(Solid electrolyte interphase, SEI)，進而提升循環穩定性。吡咯烷離子液體中陽離子部分的非極性脂肪鏈能夠產生疏鋰現象，使鋰金屬沉積均勻，避免有優選位點的發生而造成鋰枝晶形成，而陰離子部分的 FSI-離子中的 S-F 鍵能夠輕易的被破壞，進而形成 LiF，而此化合物已被證實能夠穩定 Li 金屬，在此也量測 LiFSI/PMPFSI 的離子導率，約為 3.29×10-3 S/cm，具有良好的離子導率能在界面傳輸。本研究比較未經修飾的 LLZTO 及使用液態修飾劑(碳酸酯類電解液、丁二腈基電解液、吡咯烷離子液體)修飾後的電化學性質，在長時間充放電循環中，利用傳統碳酸酯基液態電解質修飾的界面極不穩定，不僅電壓上升急劇，拆解電池後也發現固態電解質上具有蜘蛛網狀的鋰枝晶分佈，而使用 LiFSI/PMPFSI 修飾之電池，能夠持續循環 150小時以上。透過 XPS 分析，證明經由離子液體修飾的 SEI 膜具有 LiF、Li3N成份，這種液態修飾的 SEI 顯示了與固態電解質 LLZTO 兼容的界面，同時也是優異的電子阻擋層，能阻止固態電解質被鋰金屬還原，此項研究對於固態鋰電池(SSLMB, Solid-state lithium metal battery )至關重要。

摘要(英)

This study utilized hot-pressed Li6.75La3Zr1.75Ta0.25O12 (LLZTO) ceramic electrolyte and employed an ionic liquid (LiFSI/PMPFSI) as a modifier to form a stable SEI (solid-electrolyte interphase) rich in LiF, thereby enhancing cycling stability. The S-F bond of FSI- ions in the ionic liquid can be easily broken,leading to the formation of LiF. This compound has been proven to stabilize Li metal. The ionic conductivity of LiFSI/PMPFSI was also measured and found to be approximately 3.29×10-3 S/cm, exhibiting good ion conductivity for interfacial transport. Additionally, the non-polar fatty chains in the pyrrolidinium-based ionic
liquid can create a “lithiophobic effect”, promoting uniform deposition of lithium metal and preventing the formation of preferential nucleation sites and lithium dendrites. This study compared unmodified LLZTO with LLZTO modified using liquid modifiers (conventional electrolyte, SN-based electrolyte, ionic liquid) and measured the critical current density(CCD).
During long-term charge-discharge cycling, it was observed that the interface modified with the conventional carbonate-based liquid electrolyte was highly unstable. Not only did the voltage rise sharply, but post-disassembly of the battery revealed a spiderweb-like distribution of lithium dendrites on the solid-state electrolyte. In contrast, batteries modified with LiFSI/PMPFSI were able to cycle continuously for over 150 hours. XPS analysis confirmed the presence of LiF and Li3N components in the SEI film modified by the ionic liquid, demonstrating the compatibility of the interface with the solid-state electrolyte LLZTO. This research underscores the critical importance of such interfaces for Solid-State Lithium Metal Batteries (SSLMB).

關鍵字(中)

★ 離子液體
★ 吡咯烷離子液體
★ 石榴石型電解質
★ 鋰離子電池
★ 氟化鋰

關鍵字(英)

★ Ionic liquid electrolyte
★ Pyrrolidinium Ionic Liquids
★ Garnet-type electrolyte
★ Lithium-ion battery
★ LiF

論文目次

摘要 I
誌謝 IV
目錄 V
圖目錄 IX
表目錄 XII
第一章、前言 1
第二章、文獻回顧 2
2.1. 鋰離子電池簡介 2
2.1.1. 鋰電池之結構組成 2
2.1.2. 鋰電池工作原理 3
2.1.3. 固態電解質界面 4
2.2. 固態電解質 7
2.2.1. LISICON結構 9
2.2.2. NASICON 10
2.2.3. 鈣鈦礦結構 (Perovskite Type) 11
2.2.4. 石榴石結構(Garnet Type) 12
2.3. LLZO基電解質的發展與挑戰 13
2.3.1. 提高離子導電率 13
2.3.2. 電池失效機制 15
2.3.3. 界面修飾方法 18
2.4. 離子液體 20
2.4.1. 離子液體陰陽離子組合 21
2.4.2. 離子液體的應用 23
2.4.3. 離子液體修飾機制 28
2.5. 研究動機 31
第三章、實驗方法 32
3.1. 實驗藥品 32
3.2. 實驗方法 33
3.2.1. LLZTO電解質製備 33
3.2.2. 傳統型液態電解液製備 33
3.2.3. 丁二腈基電解質製備 34
3.2.4. 離子液體配置 34
3.2.5. 電池組裝 35
3.3. 材料分析與鑑定 37
3.3.1. X光繞射儀 (X-ray diffraction, XRD) 37
3.3.2. 掃描式電子顯微鏡(Scanning electron microscopy, SEM) 37
3.3.3. 拉曼光譜儀(Raman Spectrometer) 38
3.3.4. X射線光電子能譜（X-ray photoelectron spectroscopy，XPS） 38
3.4. 電化學分析 39
3.4.1. 電化學阻抗圖譜 (Electrochemical impedance spectroscopy) 39
3.4.2. 線性掃描伏安法(Linear Sweep Voltammetry, LSV) 39
3.4.3. 界面穩定性測試 40
第四章、結果與討論 41
4.1. LLZTO錠片之材料特性分析 41
4.1.1. 燒結後電解質錠片之相分析 41
4.1.2. SEM表面形貌分析 42
4.1.3. 相對密度 43
4.1.4. 交流阻抗分析 44
4.2. 離子液體之材料特性分析 46
4.2.1. 工作電位窗分析 46
4.2.2. 交流阻抗分析 47
4.3. 界面修飾對固態電解質之影響 48
4.3.1. 化學穩定性測試 48
4.3.2. 臨界電流密度分析 50
4.3.3. 長時間恆電流充放電分析 52
4.3.4. SEM表面形貌分析 54
4.3.5. XPS表面元素分析 56
4.3.6. 電池失效機制 58
第五章、結論 60
參考文獻 61

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指導教授

李勝偉(Sheng-Wei Lee)

審核日期

2023-10-16

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