臺灣博碩士論文加值系統

鋰電池受限於內部的液態電解質易燃、漏液等問題，因此衍生出安全性高的固態電解質的研究來解決此疑慮。本研究利用導離子型高分子 ( 導離子高分子 ) 與無機陶瓷材料 ( Ceramic ) 進行混摻，也混摻鋰鹽，製備出複合固態電解質。XRD分析中，可以確認複合固態電解質依然保有陶瓷材料的晶型，有助鋰離子在陶瓷材料內部傳遞；其在60 oC測得離子傳導度3.80 x 10-4 S/cm。複合固態電解質之電化學穩定窗口可達5.0 V以上，鋰離子遷移數亦測得0.243。本研究導入三明治結構電解質概念，塗佈Polymer層於複合膜兩面，旨在改善電解質與電極的接觸性。本研究製備之複合固態電解質在對稱鋰金屬0.1 mA cm-2電流充放電測試下，經過850小時後，電壓變化不大，顯示其擁有高穩定性。本研究在60 oC進行電池充放電能力測試，在1 C放電速率下測得123.51 mAh/g，保有86.54 %的電容維持率 ( 相對於0.1 C )。於電池循環壽命測試中 ( 0.2 C充電、0.5 C放電 ) 下，經過了 150圈後其仍有電容維持率79.04 %，庫倫效率為99.32 %。電池經過150圈充放電測試後，透過SEM影像觀察充放電鋰金屬表面，相較於一般液態電解質生成明顯鋰枝晶層，本研究製之三明治結構電解質 ( S.W.E ) 無明顯鋰枝晶生成。由上述所述可歸納本研究所製備之電解質具備優異的電化學特性，亦能夠抑制鋰枝晶刺穿電解質，將其應用在鋰電池中，可望提升電池的安全性。

In this study, we used Ceramic Ion Conductor LATP to mix with Ionic Conducting Polymer to fabricate a high safety Polymer in Ceramic Composite Solid State Electrolytes (PIC-CSE). We found that PIC-CSE demonstrated good results: Ionic Conductivity hit 6.58 x 10-5 S/cm2 at 60 oC, high decomposition temperature 287.08 oC, strong mechanical strength 2736.93 MPa, large electrochemical window up to 5V and the lithium transference number was 0.243.

To elevate the electrochemical performance, a thin layer of polymer was coated on both side of PIC-CSE, so it denominated as PIC Sandwiched Structure Electrolyte (PIC-SWE). PIC-SWE showed good capacity of 123.51 mAh/g under 1.0C discharging. Moreover, from the cycle life, we collected the capacity retention was 79.04 % while the columbic efficiency was 99.32 % after 0.2 C Charging, 0.5 C Discharging test for a continuous 150th cycles. Besides, the high stability with no short circuit occurred under Lithium Symmetry 0.1mA cm-2 Charging-Discharging test after 850 hours. To understand the lithium surface morphology, SEM was carried out and there wasn’t observe obvious dendrite growth compared to commercialized liquid electrolyte Lithium Batteries. As a conclusion, these high safety PIC-SWE is believed to have high potential to be commercialized.

中文摘要 i
Abstract iii
誌謝 xiv
表目錄 xviii
圖目錄 xix
第一章 緒論 1
1.1前言 1
1.2 鋰電池簡介 2
1.3電解質 4
1.4 研究動機 5
第二章 文獻回顧 6
2.1 鋰離子電池基本工作原理 6
2.2 正極材料 7
2.2.1 磷酸鋰鐵LiFePO4 ( LFP ) 7
2.2.2 鋰鈷氧LiCoO2 ( LCO ) 9
2.2.3 鋰鎳鈷錳氧Li(NixCoyMnz)O2（ NCM ） 10
2.3 陶瓷材料 11
2.3.1 NASICON 結構 12
2.3.2 Garnet Type 石榴石結構 14
2.3.3 Perovskite-type 鈣鈦礦結構陶瓷材料 16
2.3.4 LISICON-type 陶瓷材料 18
2.4 陶瓷-高分子複合型電解質 ( Ceramic-Polymer Composite Electrolyte ) 19
2.4.1 Polymer in Ceramic ( PIC ) 複合型固態電解質 20
2.5 Polymer/Composite Electrolyte/Polymer Sandwiched Structure Electrolyte 高分子/固態電解質/高分子 三明治結構電解質 26
第三章 實驗 29
3.1 實驗藥品與材料 29
3.2儀器設備 30
3.3 樣品製備 31
3.3.1 PIC複合電解質製備方法 ( PIC-Film ) 31
3.3.2 Polymer/PIC Composite Electrolyte/Polymer Sandwiched Structure Electrolyte (S.W.E) 三明治結構電解質 33
3.4 鋰電池之製備與組裝 34
3.4.1 製備LiFePO4 正極 34
3.4.2 鈕扣型電池組裝 34
3.5 材料性質分析與鑑定 35
3.5.1 傅立葉轉換紅外線光譜儀（ FT-IR ） 35
3.5.2 X-射線繞射光譜儀 ( XRD ) 35
3.5.3 熱重分析儀 ( TGA ) 35
3.5.4 掃描式電子顯微鏡 ( SEM ) 36
3.5.5 多功能掃描探針顯微鏡 ( Scanning Probe Microscopy, SPM ) 37
3.5.6 流變性質測試 ( Rheological properties ) 38
3.5.7 穿透式電子顯微鏡 ( TEM ) 38
3.5.8 孔隙率計算 ( Porosity ) 38
3.6 電化學測試 39
3.6.1 線性掃描伏安法 ( Linear Sweep Voltammetry, LSV ) 39
3.6.2 離子傳導度 ( Ionic Conductivity ) 39
3.6.3 電化學阻抗頻譜法 ( EIS ) 40
3.6.4 電池充放電能力測試 ( C-Rate Test ) 41
3.6.5 電池循環壽命測試 ( Cycle Life Test ) 42
3.6.6 對稱鋰金屬時效穩定分析 ( Symmetry Li Ageing Test ) 42
3.6.7 對稱鋰金屬電池循環穩定性分析 ( Symmetry Li Cycle Stability Test ) 43
3.6.8 鋰離子遷移數之量測 ( Lithium Transference Number ) 43
第四章 結果與討論 44
4.1 導離子高分子與交聯劑合成鑑定與分析 44
4.1.1 傅立葉轉換紅外線光譜分析 ( FT-IR ) 44
4.1.2 X-射線繞射光圖譜 ( XRD ) 45
4.1.3穿透式電子顯微鏡圖譜 ( TEM ) 46
4.1.4 熱重分析 ( TGA ) 47
4.1.5 多功能掃描探針顯微鏡 ( SPM ) 49
4.1.6 PIC複合電解質之儲存模量與損失模量 50
4.1.7 電解質之截面分析 52
4.2 對稱鋰金屬時效穩定分析 ( Symmetry Li Ageing Test ) 55
4.3 對稱鋰金屬電池循環穩定性分析 60
4.4 線性掃描伏安法 ( LSV ) 65
4.5 離子傳導度 66
4.6 鋰離子遷移數分析 70
4.7 電池充放電能力測試 ( C-Rates Test ) 74
4.8 電池循環壽命測試 ( Cycle-Life Test ) 81
4.9 循環充放電圈數阻抗圖 ( Cycle Resistance Test ) 86
4.10 循環充放電圈數阻抗圖擬合分析 90
4.11 鋰金屬表面分析 93
第五章 結論 95
第六章 參考文獻 96

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