應用丁二腈基離子導體修飾PVDF-HFP 複合聚合物電解質與鋰電極界面之高穩定鋰離子電池

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姓名

羅時廷(Shih-Ting Lo) 查詢紙本館藏

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材料科學與工程研究所

論文名稱

應用丁二腈基離子導體修飾PVDF-HFP 複合聚合物電解質與鋰電極界面之高穩定鋰離子電池
(PVDF-HFP based composite polymer electrolyte and Li electrode interface modification by succinonitrile-based ionic conductor in high stable Li-ion battery)

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摘要(中)

本研究採用Li0.33La0.557TiO3(LLTO)奈米線複合PVDF-HFP (Poly(vinylidene fluoride-co-hexafluoropropylene)製備陶瓷複合電解質，以此來降低聚合物基體的結晶度，提升Li離子遷移率。LLTO奈米線可以形成連續的通道，能提供鋰離子連續性的傳遞，離子導率提升至1.50 x 10-4S cm-1。為了改善PVDF-HFP與Li界面的副反應，本研究提出少量LITFSI/FEC/SN離子導體修飾界面，以此提升LiF在固態電解質介面層(SEI)的比例，透過提升LiF含量來完全抑制PVDF-HFP與Li的副反應。在長時間恆電流循環充放電過程，電壓維持穩定並且持續560小時後，沒有發現副反應的跡象，與傳統液態電解質修飾界面相比提升約41 %穩定性。在恆電流循環後，從SEM表面影像顯示當CPE有副反應時，在Li表面有大量鋰樹枝晶與死鋰生成，而CPE沒有副反應時，Li表面平整且均勻。透過XPS分析CPE與Li表面元素分析證明SNE修飾CPE與Li之界面可以完全抑制副反應。此外，LFP|SNE|CPE|SNE|Li全電池在0.2 C下循環100圈後，比電容量仍保持在134 mAh g-1，庫侖效率為仍保持在98.5%，幾乎沒有容量損失（5 th：135.4 mAh g-1 和 100 th：134 mAh g-1）。這項研究顯示離子導體和兼容的界面，對 ASSLMB(All-solid-state lithium-metal battery)至關重要，特別是對於界面處的穩定性。

摘要(英)

In this study, Li0.33La0.557TiO3(LLTO) nanowires were used as ceramic fillers in PVDF-HFP-based electrolytes to reduce the crystallinity of the polymer matrix. The LLTO nanofibers also provide continuous channels that facilitate Li+ transport. The ionic conductivity were increased to 1.50*10-4 S-cm-1, about 10 times higher than that of the pure PVDF-HFP electrolyte without LLTO. We further proposed a composite polymer electrolyte using plastic superionic conductor succinonitrile-based electrolyte (LITFSI/FEC/SN, SNE), where little amounts of succinonitrile-based conductor were applied at the interface between Li electrode and PVDF-HFP-based composite polymer electrolyte. The addition of FEC to SNE increased the ratio of lithium fluoride (LiF) in the solid electrolyte interface (SEI) and inhibited the side reaction of PVDF-HFP. In the long-term galvanostatic cycle charge-discharge testing, the voltage remained stable for 560 hours and the stability improved about 41% compared to LE-modified CPE. The XPS analysis indicated that the side reactions were completed inhibited after SNE modification of CPE. Moreover, the LFP|SNE|CPE|SNE|Li cell has a discharge specific capacity of 134 mAh g−1 at 0.2 C after 100 cycles and a Coulombic efficiency of 98.5% without virtually capacity loss (135.4 mAh g−1 after 5 cycles and 134 mAh g−1 after 100 cycles). This work demonstrated that the super-conductive electrolyte and compatible interface are both crucial for improving ionic conductivity and SEI　stability in a high performance ASSLMB.

關鍵字(中)

★ 鋰離子電池
★ 聚偏氟乙烯-六氟丙烯
★ 丁二腈
★ 複合聚合物電解質
★ 氟代碳酸乙烯酯
★ 氟化鋰

關鍵字(英)

★ Lithium-ion battery
★ Poly(vinylidene fluoride-co-hexafluoropropylene)
★ Succinonitrile
★ Composite polymer electrolyte
★ Fluoroethylene carbonate
★ Lithium fluoride

論文目次

摘要 I
Abstract II
誌謝 III
目錄 IV
圖目錄 VIII
表目錄 XI
第一章、前言 1
第二章、文獻回顧 2
2.1. 固態聚合物電解質 2
2.1.1. 聚環氧乙烷(PEO) 2
2.1.2. 聚偏氟乙烯(PVDF) 3
2.2. PVDF基電解質發展 3
2.2.1. 凝膠聚合物電解質(GPE) 3
2.2.2. 全固態聚合物電解質(SPE) 4
2.3. PVDF-HFP基固態複合電解質之結構設計 5
2.3.1. PVDF-HFP基固態複合電解質 5
2.3.2. 陶瓷填料之LLTO奈米線 6
2.4. PVDF基複合聚合物電解質之界面優化 7
2.4.1. 少量液態電解液降低界面阻抗 8
2.4.2. 添加LiF抑制副反應 8
2.4.3. 界面修飾之傳統型液態電解質 9
2.4.4. 界面修飾之丁二腈基電解質 11
2.4.5. 研究動機 12
第三章、實驗方法 14
3.1. 實驗藥品 14
3.2. 實驗方法 15
3.2.1 LLTO之靜電紡絲與煅燒製程 15
3.2.2. LLTO之粉末合成與煅燒製程 15
3.2.3. 製備PVDF-HFP基複合聚合物電解質 16
3.2.4. 丁二腈基電解質 17
3.2.5. 傳統型液態電解質 17
3.3. 材料分析與鑑定 17
3.3.1. X光繞射儀 (X-ray diffraction, XRD) 17
3.3.2. 掃描式電子顯微鏡(Scanning electron microscopy, SEM) 17
3.3.3. 穿透電子顯微鏡(Transmission Electron Microscopy, TEM) 18
3.3.4. X射線光電子能譜（X-ray photoelectron spectroscopy，XPS） 18
3.4. 電化學分析與電池組裝 19
3.4.1. 電化學阻抗譜 (EIS) 19
3.4.2. 恆電流充放電(Chronopotentiometry) 19
3.4.3. 鈕扣電池組裝 20
第四章、結果與討論 21
4.1.　LLTO奈米線之材料特性分析 21
4.1.1. 初紡及煅燒後之LLTO陶瓷奈米線分析 21
4.1.2. TEM表面形貌分析 22
4.2.　PVDF-HFP複合固態電解質之材料特性分析 23
4.2.1. SEM形貌分析 23
4.2.2. 交流阻抗分析 24
4.3. 界面修飾對複合聚合物電解質之影響 26
4.3.1. 交流阻抗分析 26
4.3.2. 恆電流充放電分析 27
4.3.3. 恆電流充放電後之交流阻抗分析 30
4.3.4. SEM表面形貌分析 31
4.3.5. XPS表面元素分析 33
4.4.　PVDF-HFP基複合聚合物電解質之全電池電性 39
4.4.1. 循環伏安法 39
4.4.2. 複合聚合物電解質全電池之倍率性能 40
4.4.3. 複合聚合物電解質全電池之長時間循環性能 41
第五章、結論 43
參考文獻 44

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指導教授

李勝偉(Sheng-Wei Lee)

審核日期

2022-8-30

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