二次電池的技術開發是電子產業發展歷史的里程碑，然而有機系液態電解質具有可燃及爆炸的安全問題，因此帶動不可燃的固態電解質作為替代品的研究。固態電解質應用於全電池時，其與電極材料之間存在高界面阻抗而降低離子傳導率。因此本研究目標在於改善固態電解質於室溫中的離子傳導率以及化學穩定性，並解決應用時所帶來的高界面阻抗問題。在本研究中，摻雜鈣離子於鈉離子超導離子體結構（sodium super ionic conductor, NASICON）之固態電解質中以改善鈉離子傳導性，並加入高分子材料製作複合固態電解質薄膜，降低其與電極材料之間的介面阻抗，最後進行全固態電池的穩定性測試。當鈣離子摻雜量為X = 0.1（Na3+2XCaXZr2-XSi2PO12）時，其室溫下之離子傳導率可由 1.4 × 10−4提升至 1.8 × 10−4 （S cm−1），顯示其為具有潛力之鈉離子固態電解質。本研究並將此陶瓷粉末與高分子混合成複合式固態電解質薄膜，可提升此離子傳導率至2.5 × 10−4 （S cm−1）。在全固態電池測試方面，第一圈之放電電容達44.9 mAh g−1，充放電50圈後循環維持率為70%，而以液態電解質製備之全電池在充放電50圈後之循環維持率為66.3%，顯示此全固態電池具有較液態全電池更高之循環穩定性。此結果顯示Na3+2XCaXZr2-XSi2PO12固態電解質具有發展全固態鈉離子電池之潛力。

The invention of secondary batteries technology is a milestone in the electronic industry. However, the liquid organic electrolytes suffer from safety issues such as flammability and explosion. This gives rise to the progress of new solid electrolytes as non-flammable alternatives. When applying solid-state electrolytes for practical use in all-solid-state batteries, the high contact resistance which is between electrode and electrolyte results in low ionic conductivity. Therefore, our study aims to develop a chemically stable sodium ion solid electrolyte with high ionic conductivity at room temperature and solves the issue of high interfacial resistance. In this study, we improved a sodium ionic solid electrolyte (sodium super ionic conductor, NASICON) by cation substitution, and used polymer composite film to reduce the interface resistance between electrolyte and electrodes. Finally, the stability test of full cells was carried out. When the amount of Ca-doped was X = 0.1 (Na3+2XCaXZr2−XSi2PO12), the ionic conductivity was increased from 1.4 × 10−4 to 1.8 × 10−4 (S cm−1) at room temperature, revealing that it is a potential sodium solid-state electrolyte. The ceramic powder was mixed with the polymer to form composite solid-state electrolyte membrane, and the ionic conductivity increased to 2.5 × 10−4 (S cm−1). In the test of all solid-state batteries, the discharge capacity in the first cycle was 44.9 mAh g−1 and the cycling retention was 70.0% after 50 cycles, while the cycling retention of the full cell with liquid-state electrolyte was 66.3%. This result shows that the stability of solid-state electrolyte is higher than the liquid-state electrolyte, and demonstrating that Na3+2XCaXZr2−XSi2PO12 is a potential solid state electrolyte for all solid-state sodium-ion batteries.

摘要 I
Abstract II
致謝 III
目錄 VI
圖目錄 IX
表目錄 XIII
第一章 前言 1
第二章 文獻回顧及原理簡介 2
2.1鈉離子固態電池原理與簡介 2
2.2鈉離子固態電解質介紹 3
2.3 NASICON結構之鈉離子氧化物固態電解質簡介 5
2.4 NASICON結構之鈉離子氧化物固態電解質 7
2.5電化學分析方法 9
2.5.1線性掃描伏安法（Linear Sweep Voltammetry, LSV）9
2.5.2交流阻抗分析原理（Electrochemistry Impedance Spectroscopy, EIS）10
第三章 實驗流程與研究方法 14
3.1實驗架構 14
3.2實驗藥品與器材 16
3.3實驗流程 17
3.3.1 合成Na3Zr2Si2PO12與摻雜Ca之Na3Zr2Si2PO12鈉離子固態電解質 17
3.3.2 Ca-NZSP/PEO複合鈉離子固態電解質薄膜製備 19
3.3.3正極材料與極片的製備 20
3.2.4全固態鈉離子電池組裝 21
3.4實驗儀器分析介紹 21
3.4.1 X光繞射分析儀（X- Ray Diffractometer, XRD）21
3.4.2場發射掃描式電子顯微鏡（Cold Field emission Scanning Electron Microscope, CFE- SEM） 23
3.4.3 X光光電子能譜儀（X-ray Photoelectron Spectroscopy, XPS）24
3.4.4線性掃描伏安法（Linear Sweep Voltammetry, LSV） 25
3.4.5交流阻抗分析測試（Electrochemistry Impedance Spectroscopy Analysis）26
第四章 實驗結果與討論 28
4.1以溶膠凝膠法（方法一） 合成NZSP固態電解質 28
4.2以溶膠凝膠法（方法二）合成Ca-NZSP固態電解質 34
4.2.1 NZSP合成: 不同燒結溫度與時間的影響 34
4.2.2於鍛燒溫度800 °C下合成Ca-NZSP:不同Ca摻雜比例與燒結溫度的影響 37
4.2.3於鍛燒溫度900 °C下合成Ca-NZSP:不同Ca摻雜比例與燒結溫度的影響 43
4.2.4固態電解質之材料性質總結 51
4.3Ca(0.1)-NZSP/PEO複合鈉離子固態電解質薄膜 53
4.4固態鈉離子電池測試 56
第五章結論 60
第六章未來展望 61
本研究相關之發表 62
參考文獻 63

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